Beruflich Dokumente
Kultur Dokumente
Section, Sitamarhi
XII Chemistry Advanced Study Material
Inorganic Chemistry
1 Atomic Structure II
2 Periodic Classification II
3 p Block Elements
4 d Block Elements
5 f Block Elements
6 Coordination Compounds and Bio-Coordination Compounds
7 Nuclear Chemistry
Physical Chemistry
8 Solid State II
9 Thermodynamics II
10 Chemical Equilibrium I
11 Chemical Kinetics II
12 Surface Chemistry
13 Electro Chemistry
Organic Chemistry
14 Isomerism in Organic Chemistry
15 Hydroxy Derivatives
16 Ethers
17 Carbonyl Compounds
18 Carboxylic Acids
19 Organic Nitrogen Compounds
20 Biomolecules
21 Chemistry in Action
Session : 2015-17
1. ATOMIC STRUCTURE - II
Learning Objectives
( To study the dual property of electron and understand the
property through experiments.
( To derive the de-broglie relation and learn its significance.
( To learn Heisenbergs uncertainty principle.
( To study Molecular Orbital Theory and its application to
Homodiatomic and Heterodiatomic molecules.
( To understand the concept of Hybridisation and Hybridisation of
s, p and d orbitals.
Dalton(1808)
: Discovery of atom
2.
3.
Goldstein(1886)
4.
Sir.J.J.Thomson(1897)
5.
Rutherford(1891)
6.
MaxPlanck(1901)
7.
RobertMillikan(1909)
8.
H.G.J.Mosely(1913)
9.
Niels Bohr(1913)
11. de-Broglie(1923)
12. Pauli(1927)
: Discovery of neutrino
: Discovery of neutron
15. Anderson(1932)
: Discovery of positron
16. Fermi(1934)
: Discovered antineutrino
: Discovered mesons
18. Segre(1955)
: Discovered antiproton
In 1803, John Dalton, proposed his atomic theory. He suggested that atoms
were indivisible solid spheres.
Rutherford suggested the planetary model, but this model was rejected.
In 1913, Neils Bohr proposed that electrons revolve around the nucleus in
a definite orbit with a particular energy. Based on the facts obtained from
spectra of hydrogen atom, he introduced the concept of energy levels of
atom.
From the study of quantum numbers, various rules are put forward for
filling of electrons in various orbitals by following
Aufbau principle
In 1921 Burry and Bohr gave a scheme for the arrangement of electrons in
an atom. Further the nature of electron (s) is studied.
WAVE
Nickel crystal
Fig.1.1 Electron diffraction experiment by Davisson and Germer
Since X-rays have wave character, therefore, the electrons must also have
wave character associated with them. Moreover, the wave length of the electrons
as determined by the diffraction experiments were found to be in agreement with
the values calculated from de-Broglie equation.
From the above discussion, it is clear that an electron behaves as a wave.
ii)
Thomsons experiment
G.P. Thomson in 1928 performed experiments with thin foil of gold in place
of nickel crystal. He observed that if the beam of electrons after passing through
the thin foil of gold is received on the photographic plate placed perpendicular to
the direction of the beam, a diffraction pattern is observed as before (Fig. 1.2).
This again confirmed the wave nature of electrons.
5
Thin foil
of Gold
Fig. 1.2 Diffraction of electron beam by thin foil of gold (G.P. Thomson
experiment)
b)
ii)
iii)
The phenomenon of Black body radiation and Photoelectric effect also prove
the particle nature of radiation.
6
...(i)
...(ii)
or
h.c/
=
=
=
=
mc2
c/
mc2
h / mc
de Broglie pointed out that the above equation is applicable to any material
particle. The mass of the photon is replaced by the mass of the material particle
and the velocity c of the photon is replaced by the velocity v of the material
particle. Thus, for any material particle like electron, we may write
= h / mv or = h / p
where mv = p is the momentum of the particle.
The above equation is called de Broglie equation and is called de
Broglie wavelength.
Thus the significance of de Broglie equation lies in the fact that it relates the
particle character with the wave character of matter.
Louis de-Broglies concept of dual nature of matter finds application in the
construction of electron microscope and in the study of surface structure of solids
by electron diffraction. The de-Broglies concept can be applied not only to
electrons but also to other small particles like neutrons, protons, atoms, molecules
etc.,
7
This value of can be measured by the method similar to that for the
determination of wave length of X-rays.
ii)
v
= __
v
h
__ = ___
mv
mv2
or = ___
h
2 5.85 10-25 J
____________
6.626 10-34 JS
Problem 2
Calculate the de-Broglie wavelength of an electron that has been accelerated
from rest through a potential difference of 1 kV
Solution
Energy acquired by the electron (as kinetic energy) after being accelerated
by a potential difference of 1 kV (i.e 1000 volts)
= 1000 eV
= 1000 1.609 10-19 J, (1 eV) = 1.609 10-19 J)
(Energy in joules = Charge on the electron in coulombs Pot. diff. in volts)
= 1.609 10-16 J
i.e. Kinetic energy
1
2
16
mv = 1.609 10 J
2
or
1
9.110 31 v 2 = 1.609 10 16 J
2
or
v 2 = 3.5361014
or
v = 1.88 10 7 ms 1
h
6.626 10 34
=
mv 9.110 31 1.88 10 7
= 3.87 10-11 m
9
Problem 3
Calculate the wavelength associated with an electron (mass 9.1 10-31 kg)
moving with a velocity of 103m sec-1 (h=6.626 10-34 kg m2 sec-1).
Solution
Here we are given
m = 9.1 10-31 kg
v = 103 m sec-1
h = 6.626 10-34 kg m2 sec-1
h
6.626 1034
=
=
mv (9.11031 ) 103
= 7.25 10-7 m
Problem 4
A moving electron has 4.55 10-25 joules of kinetic energy. Calculate its
wavelength (mass = 9.1 10-31 kg and h = 6.626 10-34 kg m2 s-1).
Solution
Here we are given
Kinetic energy i.e.
1
mv 2 = 4.55 10 25 J
2
m = 9.1 10-31 kg
h = 6.626 10-34 kg m2 s-1
1
(9.110 31 )v 2 = 4.55 10 25
2
4.55 10 25 2
= 10 6
31
9.1 10
or
v2 =
or
v = 103 m sec1
10
h
6.626 1034
=
mv (9.11031 )103
= 7.25 10-7 m.
Problem 5
Calculate the kinetic energy of a moving electron which has a wavelength of
4.8 pm. [mass of electron = 9.11 10-31 kg, h = 6.626 10-34 Kg m2 s-1].
Solution
According to de-Broglie equation,
h
mv
v=
h
6.626 1034 kg m 2 s 1
=
= 1.516 108 ms 1
31
12
m 9.1110 kg 4.8 10 m
or
v=
h
m
1
1
Kinetic energy = mv2 = 9.111031 kg (1.516108 ms1 ) 2
2
2
h
p
or
p =
h
For particle A, p A =
A
11
But,
pB =
h 1 h
=
B 2 A
A
1
=
B
2
But
or
B = 2A
A = 5 10-8 m
B = 2A = 2 5 10-8 m = 10 10-8 m = 10-7 m.
2.
3.
4.
What must be the velocity of a beam of electrons if they are to display a deBroglie wavelength of 100?
[Ans. : 7.25 104 ms-1]
5.
6.
7.
8.
9.
A moving electron has 4.9 10-25 joules of kinetic energy. Find out its de Broglie wavelength (Given h = 6.626 10-34 Js; me = 9.1 10-31 kg).
[Ans. : 7 10-7 m]
h
4
13
Example 1
Calculate the uncertainty in the velocity of a wagon of mass 3000kg
whose position is known to an accuracy of 10 pm (Plancks constant =
6.626 1034 Kg m2 s-1.
Solution : ere we are given
m
= 3000 kg
x = 10 pm
= 10 10-12 m = 10-11 m
y uncertainty principle,
v =
h
4 m x
6.626 10 34
=
22
4 3000 10 11
7
10-27ms-1
= 1.76
Example 2
Calculate the uncertainty in the position of an electron if the uncertainty in its
velocity is 5.7 105 m/sec (h = 6.626 10-34 kg m2 s-1, mass of the electron
= 9.1 1031 kg).
Solution:
h
4
h
4 m
14
6.626 10 34
22
9.110 31 5.7 105
7
= 1.0 10-10 m
i.e Uncertainty in position = 10-10 m.
4
2.
3.
4.
5.
the light has wave nature at one time and particle nature at another time. Therefore,
light has a kind of duality.
The idea of deBroglie wave nature waves or deBroglie matter waves is
based on the fact that light has both wave and particle nature. Hence particle like
electron or proton can also be considered to be particle with wave nature.
Einsteins relations which connect the particle and wave aspects in light
quanta
h
(1)
would be satisfied for de Broglie matter waves as well. Therefore the relations,
Eq.(1), are often called Einstein-de Broglies relations.
E = h,
p=
If we apply these relations to the case of the Bohr model of the hydrogen
atom, we can well understand its possibility as follows. If we consider that the
electron in a hydrogen atom moves at constant speed along a circular orbit around
the nucleus (proton), the quantum condition in Bohrs quantum theory is written
as Eq(2). By using Einsteins relation p = h/ in this equation, the quantum
condition is written
2a = n,
(n = 1, 2, 3, ....)
(2)
This equation means that the circumference of the circular orbit of the electron
must be a integral multiple of the wavelength of de Broglie wave. In other word,
de-Broglie wave accompanying the motion of the electron should be continuous.
Therefore, we can easily understand the quantum condition that determines the
stationary states by considering the continuity of de Broglie waves (See the
following figure).
Bohrs quantum condition. The condition
for stationary states
The circumference of the circular orbit of
the electron should be an integral multiple of
the wavelength of de Broglie wave,
otherwise the wave cannot be smoothly
continuous.
16
(2)
- 1312
kJ mol 1
2
n
1312
= -328 kJ mol-1
22
E = E 2 E1 = [328 (1312)] kJ = 984 kJ mol1
E
N
=
17
984103 J/atom
6.02371023
E
c
= h = h ;
N
Nh1c
E
2.181018 J atom1
0.24210 J atom =
n2
18
n=3
Example 3
Calculate the ionisation energy of hydrogen atom as well as energy needed
to promote its electron from first energy level to third energy level.
Solution
The energy of electron in hydrogen atom is given by the expression,
i)
n = ,
E = 0
ii)
1312
= 1312 kJ mol 1
12
E3 =
1312
= 146 kJ mol 1
32
Thus, p-orbitals have dumb-bell shape and have directional character. The
probability of finding the electron is equal in both the lobes. The p-orbitals of
higher energy levels have similar shapes although their size are bigger.
Shape of d-orbitals
For d-subshell, l = 2, there are five values of m namely -2, -1, 0, 1, 2. It
20
means d- orbitals can have five orientations. These are represented by dxy, dyz,
dzx, dx2-y2 and dz2; for example, 3dxy, 3dyz, 3dzx, 3dx2-y2 and 3dz2. The dxy, dyz and
dzx orbitals have same shape i.e., clover leaf shape but they lie in XY, YZ and ZXplanes respectively.The dz2 orbital is symmetrical about Z-axis and has a dumb bell shape with a doughnut shaped electron cloud in the centre. The
dx2-y2 orbital is also clovar leaf shaped but its leaves are directed along the X and
Y- axis.
The reason for the presence of four lobes in any nd orbital lies in the fact that
the d - orbitals have two nodes, and hence two changes in algebraic sign of ,
which lead to four lobes.
y
yx
d xy
d yz
d xz
d x 2 -y 2
d z2
(v) The shapes of molecular orbitals depend upon the shapes of combining
atomic orbitals.
(vi) The bonding molecular orbitals are represented by (sigma), (pi), (delta)
and the antibonding molecular orbitals are represented by , , *.
(vii) The molecular orbitals are filled in the increasing order of their energies,
starting with orbital of least energy. (Aufbau principle).
(viii) A molecular orbital can accommodate only two electrons and these two
electrons must have opposite spins. (Pauls exclusion principle).
(ix) While filling molecular orbitals of equal energy, pairing of electrons does
not take place until all such molecular orbitals are singly filled with electrons
having parallel spins. (Hunds rule).
1.5.1 Energy level diagram for molecular orbitals
In case of homonuclear diatomic molecules, combination of two 1s atomic
orbitals of participating atoms give rise to two new molecular orbitals designated
as 1s and *1s. In the same manner the 2s and three 2p-orbitals of each atom
i.e., eight atomic orbitals can give rise to eight new molecular orbitals viz.,
2s , *2s , 2p x , *2p x , 2p y , *2p y , 2p z , *2p z .
Atomic Structure and Chemical Bonding
Energy levels of these molecular orbitals have been determined
experimentally by spectroscopic studies.The order of increasing energy in case
of the diatomic homonuclear molecules of first and second period of the periodic
table is as given below:
1s < 1s* < 2s < *2s < 2p x = 2p y < 2p z < *2p x = *2p y < *2p z
This order of energies of various molecular orbitals is valid for molecules or
ions like, H2, H2+, He2+, He2 (hypothetical), Li2, Be2 (hypothetical), B2, C2 and
N2 molecules. This energy diagram for the molecular orbitals is shown in Fig.1.7a.
However, experimental evidence for oxygen and heavier diatomic molecules have
shown that above sequence of energy levels of MOs is not correct. In case of
these elements, the order of energy levels of 2p z , 2px and 2py is reversed i.e.,
2p z has lesser energy than 2p x or 2p y . Thus, the order of increasing energy of
MOs for these molecules is as follows.
1s < 1s* < 2s < *2s < 2p z < 2p x = 2p y < *2p x = *2p y < *2p z
22
This order of energies of various MOs is valid for molecules or ions like O2,
O (super oxide ion), O22- (peroxide ion), F2 and Ne2 (hypothetical). This energy
level diagram for MOs is shown in Fig.1.7(b).
2
Bond Order =
24
Table 1.
Molecule
Bond order
Bond length
Nitrogen
945 kJ mol-1
110 pm
-1
121 pm
-1
267 pm
Oxygen
Lithium
495 kJ mol
110 kJ mol
N b = 2 and Na = 0
25
Bond order =
Nb Na 2 0
=
= 1.
2
2
i)
Nature of bond : This means that the two hydrogen atoms in a molecule of
hydrogen are bonded by a single covalent bond.
ii)
Nb = 2 and Na = 2
Nb Na 2 2
=
= 0.
2
2
As the bond order for He2 comes out to be zero, this molecule does not
exist.
Bond order =
N 2 : KK( 2s ) 2 (*2s ) 2 ( 2p x ) 2 ( 2p y ) 2 ( 2p z ) 2
Here (1s ) 2 (1s* ) 2 part of the configuration is abbreviated as KK, which
denotes the K shells of the two atoms. In calculating bond order, we can ignore
KK, as it includes two bonding and two antibonding electrons.
The molecular orbital energy level diagram of N2 is given in Fig. 1.10.
=
= 3.
Bond order = b
2
2
i) Nature of bond : A bond order of 3 means that a triple bond is present in
a molecule of nitrogen.
ii) Diamagnetic nature : Since all the electrons in nitrogen are paired, it is
diamagnetic in nature.
4. Oxygen molecule, O2. The electronic configuration of oxygen (Z = 8)
in the ground state is 1s22s22p4. Each oxygen atom has 8 electrons, hence, in O2
27
1.6
Bond order =
Nb Na 8 4
=
= 2.
2
2
HYBRIDISATION
2
sp
3
sp2
4
sp3
5
6
3
sp d sp3d2
Example
i)
BeCl2
Total valence electrons = 2 + 7 2 = 16
16
= 2(Q1 ) + zero(R 1 ) ;
8
29
X=2
7
sp3d3
Hybridisation = sp
ii)
BF3
Total valence electrons = 3 + 7 3 = 24
24
= 3(Q1 ) + zero(R 1 ) ;
8
Hybridisation = sp2
iii)
X=3
NH3
Total valence electrons = 5 + 3 = 8 ;
X=
8
=4
2
X=
8
=4
2
Hybridisation = sp3
iv) H2O
Total valence electrons = 2 + 6 = 8 ;
Hybridisation = sp3
v)
PCl5
Total valence electrons = 5 + 7 5 = 40
40
= 5(Q1 ) + zero(R 1 ) ;
8
Hybridisation = sp3d
X=5
vi) SF6
Total valence electrons = 6 + 7 6 = 48
48
= 6(Q 1 ) + 0(R 1 ) ; X = 6
8
Hybridisation = sp3d2
vii) IF7
Total valence electrons = 7 + 7 7 = 56
56
= 7(Q1) + 0(R1) ;
8
Hybridisation = sp3d3
30
X=7
18
2
= 2(Q1) + 2(R1) ;
= 1(Q2) + 0(R2) ; X = 2+1+0=3
8
2
Hybridisation = sp2
ix) NO3- ion
Total valence electrons = 5 + 3 6 = 23; Charge = -1
Total electrons = 23 + 1 = 24
x)
24
= 3(Q 1 ) + 0(R 1 ) ; X = 3
8
Hybridisation = sp2
CO32Total valence electrons = 4 + 3 6 = 22; Charge = -2
Total electrons = 22 + 2 = 24
24
= 3(Q 1 ) + 0(R 1 ) ; X = 3
8
Hybridisation = sp2
xi) SO42Total valence electrons = 6 + 4 6 = 30; Charge = -2
Total electrons = 30 + 2 = 32
32
= 4(Q 1 ) + 0(R 1 ) ; X = 4
8
Hybridisation = sp3
31
Hybridisation = sp3d2
xiii) NH4+
Total valence electrons = 5 + 4 = 9; Charge = +1
Total electrons in NH4+= 9 - 1 = 8
8
= 4(Q 1 ) + 0(R 1 ) ;
2
Hybridisation is sp3
X = 4
Examples
sp
sp2
sp3
sp3d
sp3d2
sp3d3
IF7, XeF6
32
+
2
O H
2. Water H
. In water molecule, the electronegative oxygen atom
+
forms two polar covalent bonds with two hydrogen atoms. The oxygen atom
due to its higher electronegativity acquires partial negative charge and the two
hydrogen atoms acquire partial positive charge. The negatively charged oxygen
forms two hydrogen bonds with two positively charged hydrogen atoms of two
neighbouring molecules. Each oxygen atom is tetrahedrally surrounded by four
hydrogen atoms as shown below :
O
C
O
OH
O
C
O-Nitrophenol
Salicylic Acid
34
Salicylaldehyde
Life would have been impossible without liquid water which is the result of
intermolecular H-bonding in it.
ii) Hydrogen bonding increase the rigidity and strength of wood fibres and
thus makes it an article of great utility to meet requirements of housing,
furniture, etc.
iii) The cotton, silk or synthetic fibres also own their rigidity and tensile strength
to hydrogen bonding.
iv) Most of our food materials such as carbohydrates and proteins also consist
of hydrogen bonding.
v) Hydrogen bonding also exists in various tissues, organs, skin, blood and
bones.
SELF EVALUATION
A. Choose the correct answer
1.
a)
2.
313.6
, If the value of Ei = -34.84 to which value n corresponds
n2
4
b)
3
c) 2
d) 1
En =
3.
c) de-Broglie
d) Pauli
de-Broglie equation is
a)
4.
b) Heisenberg
mv
h
b)
= hmv
c)
hv
m
d)
b) 0.529 10-10 cm
d) 0.529 10-12 cm
35
h
mv
5.
Which of the following particle having same kinetic energy, would have the
maximum de-Broglie wave length
a) -particle
c) -particle
b) proton
d) neutron
6.
If the energy of an electron in the second Bohr orbit of H-atom is -E, what
is the energy of the electron in the Bohrs first orbit?
a) 2E
b) -4E
c)
-2E
d)
4E
7.
d)
2 me4
n 2h 2
d)
sp3d
d)
sp3d3
a)
8.
9.
4 2 me 4
n 2h 2
b)
2 2 me 2
n 2h 2
c)
c)
2)
3)
Concise Inorganic Chemistry - J.D.Lec, 3rd Ed. - 1977 and 5th Ed. 2002.
37
2. PERIODIC CLASSIFICATION - II
Learning Objectives
( To recall the periodic properties Atomic/Ionic radii, Ionisation Energy,
Electron affinity and electronegativity.
( To learn the calculation of atomic and ionic radii using different
parameters.
( To study the methods of determination of ionisation potential and
differentiate I, II and III ionisation potential.
( To know how to explain the factors affecting ionisation potential with
specific examples.
( To understand the methods to determine the electron affinity and factors
affecting electron affinity.
( To analyse the various scales of electronegativity values using simple
relations.
38
Atom(g) Energy
Positive Ion(g) + Electron
The ionisation energy of an atom depends on the following factors (i) size of
the atom (ii) charge on the nucleus (iii) screening effect of inner electrons (iv)
penetration effect of electrons (v) effect of half-filled and completely filled
sublevels.
In a period, the value of ionisation potential increases from left to right with
breaks where the atoms have somewhat stable configurations. In a group, the
ionisation potential decreases from top to bottom.
2.1.3 Electron affinity
Electron affinity or electron gain enthalpy is the amount of energy released
when an isolated gaseous atom accepts an electron to form a monovalent gaseous
anion.
Atom (g) + Electron Anion (g) + Energy
39
r(A) + r(A)
d(A A) =
2 r(A)
r(A)
d(AA)
______
2
The above equation shows that in the case of homonuclear diatomic molecule
of A2 type, the covalent radius of an atom A, r(A) is equal to one half of the internuclear distance, d(A-A). Therefore, the covalent radius of an atom in a
homonuclear diatomic molecule can be obtained by dividing the internuclear
distance by two.
40
Example
1.
Cl2 molecule
The value of ClCl bond distance as found experimentally is 1.98. Thus
r(Cl) =
2.
Diamond
Thus
b.
d(C C ) 1.54
=
= 0.77
2
2
CCl4 molecule
The experimental value of d(C Cl) is 1.76
Thus
SiC
The experimental value of d(Si-C) is 1.93 . Thus,
d(Si C) =
r(Si) + r(C)
41
r(Si)
=
=
=
=
d(Si C) r(C)
1.93 r(C)
1.93 0.77 [ r(C) = 0.77 ]
1.16
Bond
H2
F2
Cl2
Br2
H3C-CH3
Bond length ()
HH
FF
ClCl
BrBr
CC
0.74
1.44
1.98
2.28
1.54
: Na+ - 2, 8
F - 2, 8
Ne type configuration
KCl crystal
: K+
Cl
Ar type configuration
- 2, 8, 8
- 2, 8, 8
Further the following two assumptions are made to assign the ionic radii.
i) The cations and anions of an ionic crystal are assumed to be in contact
with each other and hence the sum of their radii will be equal to the inter nuclear
distance between them.
r(C+) + r(A) = d (C+A)
where
r(C+)
- radius of cation, C+
r(A)
- radius of anion, A
42
(1)
1
Z (C + )
(2)
r(A )
1
Z (A )
(3)
where,
Z*(C+) & Z*(A) are the effective nuclear charges of cation (C+) and anion
(A-) respectively. On combining (2) & (3)
r(C+ )
r(A )
Z* (A )
Z* (C + )
(4)
Hence the above two equations (1) & (4) can be used to evaluate the
values of r(C+) and r(A) provided that the values of d(C+A), Z*(C+) and
Z*(A) are known.
Slater rules
The value of screening constant (S) and effective nuclear charge (Z*) can
be calculated by using Slaters rules. According to these rules the value of S
for a given electron is estimated as follows.
i) Write down the complete electronic configuration of the element and
divide the electrons into the following orbital groups starting from the inside of
the atom.
(1s) :
(4d) :
(4f)
ii) Select the electron for which the value of S is to be calculated. For this
calculation add up the contributions to S for the other electrons according to the
following rules.
43
Type of electron
i)
ii)
0.35
(or 0.30 for 1s electron)
iii)
0.85
1.00
Z* = 2.20
Example 2
Calculate the effective nuclear charge of the last electron in an atom whose
configuration is 1s2 2s2 2p6 3s2 3p5
Z = 17
Z* = Z S
= 17 [(0.35 No. of other electrons in nth shell)
+ (0.85 No. of electrons in (n 1)th shell)
+ (1.00 total number of electrons in the inner shells)]
44
(1)
K+ and Cl ions have Ar (Z=18) type configuration. The effective nuclear charge
for K+ and Cl can be calculated as follows.
K+
(1s2)
innershell
Z*(K+)
ZS
19 11.25 = 7.75
17 11.25 = 5.75
Z*(Cl-)
(2s2 2p6)
(n-1)th shell
(3s2 3p6)
nth shell
(2)
3.14
= 1.81
1.74
45
(3)
From (2)
r(K+) = 0.74 r(Cl)
= 0.74 1.81
= 1.33
r(K+) = 1.33
r(Cl) = 1.81
Ionisation potential
Ionisation energy of an element is defined as the amount of energy required
to remove the most loosely bound electron from isolated neutral gaseous atom in
its lowest energy state. The process is represented as
M
(g)
+ Energy supplied
I
1 M
+
(g)
+ e
Ionisation energy is measured in electron volts per atom (eV/atom), kilo calories
per mole (kcal/mole) or kilo joules per mole (kJ/mole).
Successive ionisation potentials
In addition to first ionisation potential (I1) defined above, second, third. etc.
ionisation potentials are also known. Second ionisation potential (I2) is the energy
required to remove one more electron from the gaseous cation, M+(g) to get the
doubly positively charged gaseous cation, M2+(g), i.e.,
M + (g) + I 2 M 2 + (g) + e
Similarly, third ionisation potential (I3) is the energy required to remove still
one more electron from M2+(g) cation to get M3+(g) cation, i.e.
M 2 + (g) + I 3 M 3 + (g) + e
Similarly ionisation potentials of higher and higher grades are also known.
Each successive ionization potential or energy is greater than the previous
one, since the electron must be removed against the net positive charge on the
ion.
46
nuclear charge, the electrons are bound with more force and hence higher energy
will be required for their removal. For instance, magnesium has higher nuclear
charge (12 protons) as compared to sodium (11 protons). Hence ionization energy
in case of magnesium is higher as compared to sodium.
Similarly the I.E. of fluorine is more than that of oxygen. It can be explained
as follows.
(i) F (Z = 9; 1s2 2s2 2px2 2py2 2pz1) is having more nuclear charge than
oxygen (Z = 8; 1s2 2s2 2px2 2py1 2pz1). In both the cases, the electron has to be
removed from the same 2p-subshell. As fluorine is having more nuclear charge
than oxygen, it means that the nucleus of fluorine will attract the outer 2p-electrons
more firmly than oxygen. Hence, first I.E. of fluorine would be more than that of
oxygen.
(c) Effect of number of electrons in the inner shells. (Screening or
shielding effect). The attractive force exerted by the nucleus on the most loosely
bound electron is atleast partially counterbalanced by the repulsive forces exerted
by the electrons present in the inner shells. The electron to be removed is thus
shielded from the nucleus by the electrons in the inner shell. Thus, the electron in
the valence shell experiences less attraction from the nucleus. Hence the ionisation
energy will be low. This is another reason why ionization energy decreases in
moving down a group.
(d) Effect of shape of orbital. The shape of orbital also influences the
ionization potential. As s-electrons remain closer to the nucleus than p-,d-, and
f-electrons of the same valence shell, the ionization energy decreases in the order
given below:
s>p>d>f
For instance, the first ionization energy of aluminium is lower than that of magnesium.
The electronic configuration of magnesium is [Ne]3s2 and that of aluminium is
[Ne] 3s2 3p1. Thus, one has to remove 3p-electron in case of aluminium and 3s
electron in the case of magnesium. But it is easier to remove the p electron than
the s-electron. Thus, the first ionization energy of aluminium is lower than that of
magnesium.
(e) Effect of arrangement of electrons. The more stable the electronic
arrangement, the greater is the ionization energy. As the noble gases have the
stablest electronic arrangements, they show maximum ionization energy.
48
Example
The I.E of Ne is greater than that of F. It can be explained as follows:
The nuclear charge of Ne (Z = 10) is more than that of F (Z = 9). Greater
the nuclear charge, greater would be the force of attraction between nucleus and
outermost electron. Hence, the first I.E. of neon would be greater than that of
fluorine.
Electron Affinity or Electron gain enthalpy (E.A.)
The electron affinity of an element may be defined as amount of energy
which is released when an extra electron enters the valence orbital of an isolated
neutral atom to form a negative ion.
Atom(g) + Electron(g) Negative ion(g) + Energy
The greater the energy released in the process of taking up the extra electron,
the greater will be the electron affinity. Thus, ionisation potential measures the
tendency of an atom to change into a cation (M M+ + le-) whereas the electron
affinity measures the tendency of an atom to change into anion (X + e- X-).
Successive Electron Affinities. As more than one electron can be
introduced in an atom, it is called second electron affinity for the addition of two
electrons and so on. The first E. A. of active non metals is positive (exothermic)
while the second E. A. even for the formation of oxide or sulphide ion is negative
(endothermic). For example, the overall E.A. for the formation of oxide or sulphide
ions has been found to be endothermic to the extent of 640 and 390 kJ mol-1
respectively.
X-(g) + e- + energy X2-(g)
It is interesting to note that the electron affinity of elements having a d10 s2
configuration has been found to be negative. This is so due to the accommodation
of the electron in the higher p-orbital (Zn = -87 kJ mol-1, Cd = -56 kJ mol-1).
Elements of group 17 possess high electron affinity. The reason for this is
that by picking up an electron halogens attain the stable noble gas electronic
configuration.
The electron affinity is expressed in kJ mol-1.
49
50
1
Size of atom
Smaller the size of an atom, greater is its electron affinity. As the size of
atom increases, the effective nuclear charge decreases or the nuclear attraction
for adding electron decreases. Consequently, atom will have less tendency to
attract additional electron towards itself. Therefore.
Electron affinity Effective nuclear charge.
In general, electron affinity decreases in going down the group and increases
in going from left to right across the period. On moving down the group atomic
size increases and on going from left to right in a period atomic size decreases.
(2) Shielding or Screening Effect
Electron affinity
1
Shielding effect
Electronic energy state, lying between nucleus and outermost state hinder
the nuclear attraction for incoming electron. Therefore, greater the number of
inner lying state, less will be the electron affinity.
(3) Electronic Configuration - The electronic configurations of elements
influence their electron affinities to a considerable extent.
Electron affinities of inert gases are zero. This is because their atoms have
stable ns2 np6 configuration in their valence shell and there is no possibility for
addition of an extra electron.
Electron affinity of beryllium, magnesium and calcium is practically zero.
This is attributed to extra stability of the fully completed s-orbitals in them. Thus,
if an atom has fully filled or half filled orbitals, its electron affinity will be low.
Example 1
The electron affinities of Be, Mg and N are almost zero because both
Be (Z = 4; 1s2 2s2) and Mg (Z = 12; 1s2 2s2 2p6 3s2) are having s orbital fully
51
filled in their valence shell. Fully filled orbitals are most stable due to symmetry.
Therefore, these elements would be having least tendency to accept electron.
Hence, Be and Mg would be having zero electron affinity.
N (Z = 7 ; 1s2 2s2 2px1 2py1 2pz1) is having half filled 2p-subshell. Half filled
sub shells are most stable due to symmetry (Hunds rule). Thus, nitrogen is having
least tendency to accept electron. Hence, nitrogen is having almost zero electron
affinity.
Example 2
Electron affinity of fluorine is less than that of chlorine. Although the
electron affinity of elements decreases down the group, yet fluorine is having less
electron affinity than chlorine because the size of F-atom (0.71 ) is very small
and has only two shells, i.e., n = 1, 2 (9F = 1s2 2s2 2px2 2py2 2pz1).
i) Because of small size of fluorine atom the 2p-subshell becomes compact.
There occurs repulsion among electrons of the valence shell and also with electron
to be added. This repulsion is responsible for less tendency of F-atom to accept
electron.
ii) Because of small size of fluorine there occurs large crowding of electrons
around the nucleus. This crowding is able to screen the nucleus. Because of this,
effective nuclear charge gets decreased. Thus, the electron is having less attraction
during addition. Hence electron affinity gets decreased.
2.5 ELECTRONEGATIVITY SCALES
Electronegativity scale is an arbitary scale. They are based on various types
of experimental data like bond energy, dipole moment, ionisation potential and
electron affinity. Most commonly used scales are
1. Paulings scale
2. Mullikens scale
3. Sandersons scale
4. Alfred and Rochows scale
Paulings scale (1932)
This scale is based on an empirical relation between the energy of a bond
and the electronegativities of bonded atoms.
52
E A B > E A A E B B
Their difference () is related to the difference in the electronegativities of
A and B according to the following equation
=
=
(or)
0.208
E A B E A A E B B
(X A X B ) 2
= XA XB
E HCl E H H E Cl Cl
=
=
134 104 36
134 61.18 =
72.82
53
0.208
X Cl X H
X Cl X H
=
=
=
=
=
0.208 72.82
1.77
1.77
1.77 + 2.1
3.87
XCl - 2.1
XCl
2.
[ XH = 2.1]
Mullikens Scale
I.E. + E.A
2
I.E. + E.A
I.E. + E.A
=
2 2.8 96.48
540
This method has an ordinary theoretical basis and also has advantage that
different values can be obtained for different oxidation states of the same element.
Disadvantage
Although Mullikens scale is less empirical than Pauling Scale, yet it suffers
from a serious disadvantage that electron affinities with the exception of a few
elements are not reliably known.
54
Problem
Calculate the electronegativity values of fluorine and chlorine on Mullikens
scale, given that (Ionisation potential) F = 17.4 eV/atom (Electron affinity) F =
3.62 ev/atom, (IP)Cl = 13.0 ev/atom and (EA)Cl = 4.0 ev
Electronegativity of fluorine
Electronegativity of chlorine
(IP) F + (EA) F
2 2.8
17.4 + 3.62
21.02
=
= 3.75
5 .6
5 .6
(IP) Cl + (EA) Cl
2 2.8
1 3 .0 + 4 .0
17
=
5 .6
5 .6
Applications of electronegativity
=
1)
= 3.03
Nature of bond
When XA = XB, i.e. XA - XB = 0, then A-B bond is non polar covalent bond
or simply covalent bond and is represented as A-B. eg. H-H bond in H2
molecule is a covalent bond and is represented as H-H bond.
ii)
When XA is slightly greater than XB, i.e. XA - XB is small, the A-B bond is
polar covalent bond and is represented as A--B+ . e.g. The O-H bonds
in H2O molecule are polar covalent bonds and are represented as O--H+,
since XO > XH and XO - XH is small.
iii)
When XA >> XB, i.e., XA - XB is very large, A-B bond is more ionic or
polar bond and is represented as A--B+, Since XA >> XB. For example
Na-Cl bond in Na Cl molecule is an ionic bond and is represented as Na+Cl(Here Cl = A and Na = B).
55
2.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
B.
16.
17.
18. Which element of the following has the highest ionisation potential?
Na, Cl, Si and Ar.
19. Describe with reasons which atom in each of the following pairs has higher
ionisation energy?
a) Mg and Al
b) B and Al
c) Al and Si
20. Which element of the following pairs of elements has higher ionisation energy?
Justify your answer
a) K or Ca b) Be or B c) I or Ba d) F or Cl
e) N or O
21. Which element of the following groups of elements has smallest ionisation
energy. Justify your answer.
a) Ca or Be
b) Ca or K
c) Cl or I
d) Be, B, C
22. Answer the following questions
a) Which element has the most positive value of electron affinity?
b) Which element has low electronegativity?
23. Mention the disadvantage of Pauling and Mulliken scale.
24. Why EA of fluorine is less than that of chlorine?
C. Answer not exceeding 60 words
25. How is atomic radii calculated from covalent bond length?
26. Explain Pauling method to determine ionic radii.
27. Explain the variation of IE along the group and period.
28. Explain the various factors that affect electron affinity.
29. How electronegativity values help to find out the nature of bonding between
atoms?
Summary
The periodicity in properties of elements are reviewed briefly. Atomic and
ionic radii of molecules are calculated by using simple examples. The factors
governing ionisation potential are explained with specific examples. The factors
affecting electron affinity are discussed briefly. The different scales of
electronegativity values are explained in detail.
References
1) Concise Inorganic Chemistry, J.D. Lee, 3rd Edition, 1977.
2) Selected Topics in Inorganic Chemistry, Wakid V.Malik, G.D.Tuli,
R.D.Madan 7th edition, 2001.
58
3. p - BLOCK ELEMENTS
Learning Objectives
( Understand the general trends in the chemistry of elements of groups
13,14,15,16,17 and 18.
( Understands the preparation, properties and the uses of potash alum.
( Knowledge about know about silicones.
( Understand the extraction of lead, properties and the uses of lead.
@ Understands the preparation, properties, uses and the structure of
halides, oxides, oxyacids and hydrides of phosphorus.
( Recognize the anomalous behavior of Fluorine.
( Understand about interhalogen compounds.
( Know about the isolation of noble gases.
( Recognises the preparation, properties and the structure of xenon
compounds.
( Appreciates the application of noble gases.
59
PERIODIC TABLE
18
n s 2 n p 1-5
He
Ne
Cl
Ar
As
Se
Br
Kr
Sn
Sb
Te
Xe
Pb
Bi
Po
At
Rn
13
14
15
16
17
12
Al
Si
Ga
Ge
In
Tl
ns2np1 n s 2 n p 2
13
14
15
16
B o ro n g ro u p
C a rb o n g ro u p
N itro g en g ro u p
O x y g en g ro u p
n s 2n p 3
17
18
n s 2n p 4
n s 2n p 5 n s 2 n p 6
p-block elements grouped with s-block elements are called as main group
elements or representative elements. There are 44 main group elements. pblock
elements occupy groups 13-18 of the periodic table including inert gases.
p-block elements play dominant part in all natural processes. Aluminium plays
vital role in aircraft and as conductors. Carbon is the backbone of all organic
compounds. Silicon chips play a vital part in computers. Nitrogen acts as a building
block of life. Molecular oxygen is a cell fuel.
60
2.
These elements include metals and non-metals with a few semi metals
(Metalloids)
3.
4.
These elements possess relatively higher ionisation energy and the value
tends to increase along the period but decrease down the group.
5.
Most of the elements show negative (except some metals) as well as positive
oxidation states (except Fluorine).
6.
Boron is a relatively rare element, accounting for only about 0.001% of the
earths crust by mass.
Gallium is remarkable for its unusually low melting point (29.7C) and
therefore generally exist as a liquid at room temperature. Its most important
use is in making gallium arsenide. This is a semi conductor material employed
in the manufacture of diode lasers for laser printers, compact disc players
and fibre optic communication devices.
61
Electronic Configuration
Group
Number
Period
Periodic
Number
Number
Boron
13
Aluminium
13
13
Gallium
31
13
Indium
49
13
Thallium
81
13
Element
2.
Both silicon and germanium are used in making modern solid state electronic
devices.
Tin and lead have been known and used since ancient times.
General Trends
Electronic configuration: The elements of this group possess ns2 np2
electronic configuration.
Atomic
Number
Electronic Configuration
Group
Number
Period
Periodic
Number
Number
Carbon
14
Silicon
14
14
Germanium
32
14
Tin
50
14
Lead
82
14
Element
63
Cl
Si
Si
OH
Si
Cl
R
HO
H 2O
Si = 0
OH
R
OH + HO
Si
OH
HO
Si
R
O
Si
OH
Si
R
O
Si
R
R
The dialkyldichlorosilane R2SiCl2 on hydrolysis gives rise to straight chain
polymers and, since an active OH group is left at each end of the chain,
polymerisation continues and the chain increases in length.
R
HO
Si
R
R
O
Si
R
O
Si
R
64
R
O
Si
R
OH
The hydrolysis of alkyl tricholorosilane RSiCl3 gives a very complex crosslinked polymer.
|
|
O
O
R
Si
Si
O
R
Si
Si
Uses
1)
Silicones act as excellent insulators for electric motors and other appliances
as they can withstand high temperatures.
2)
Straight chain polymers of 20 to 500 units are used as silicone fluids. They
are water repellent because of the organic side group. These polymers are
used in waterproofing textiles, as lubricants and as polish.
3)
Silicone rubber retain their elasticity even at low temperatures and resist
chemical attack. They are mixed with paints to make them damp-resistant.
4)
5)
Silicone oils are highly stable and non-volatile even on heating. Hence used
for high temperature oil bath, high vacuum pump etc.
Galena
PbS
Cerrusite PbCO3
Anglesite PbSO4
Lead ochre PbO
65
Extraction: Lead is mainly extracted from the sulphide ore galena. Galena
contains lead sulphide and small quantities of silver.
1.
PbS + 2O2
2 PbO + 2SO2
PbSO4
3Pb+SO2
2Pb+2SO2
Thus in this process roasting and smelting are carried out in the same furnace,
at two different temperatures.
About 90% of lead is obtained as metal, the rest passes into slag. Lead is
recovered from the slag by heating with lime and powdered coke.
66
Powdered ore
Concentration
smelting
Impure Metal
Electrolytic
refining
Liquation
Desilverisation
Pb metal +Au, Sn
Pb +Sn, Ag, Au
Purification of Lead
Lead extracted by the above method contains impurities such as silver,
copper, tin, bismuth, gold and iron. It is refined by the following processes.
a.
Liquation
The impure metal is heated on a sloping hearth. Lead melts and flows down
the slope. The infusible impurities remain on the hearth.
b.
Desilverisation
Silver is removed by either Pattinsons process or Parks process.
c.
Electrolytic refining
Very pure lead is obtained by this process.
Anode Impure lead
Cathode Very pure lead
Electrolyte Lead fluosilicate + Hydrofluosilicic Acid
(H2SiF6)
(PbSiF6)
The metallic impurities which are more electropositive than lead, such as
iron and tin, go into the solution while the rest of the impurities are thrown
down as anode mud.
67
Physical properties
1.
2.
3.
4.
Chemical properties
1.
Action of air
i)
It is unaffected by dry air but in moist air a layer of lead carbonate or lead
hydroxide is deposited on its surface which protects it from further action of
air.
When heated in air or oxygen, lead is oxidized to litharge (PbO) and red
lead (Pb3O4)
ii)
2Pb + O2 2PbO
3Pb + 2O2 Pb3O4
2.
Action of water
Lead is not attacked by pure water in the absence of air, but water containing
dissolved air has a solvent action on it due to the formation of lead hydroxide (a
poisonous substance). This phenomenon is called Plumbo solvency.
2Pb + O2 + 2H2O
2Pb(OH)2
3.
Action of acids
i)
ii)
iii)
PbCl2 +H2
H2PbCl4
chloroplumbic acid
68
Problem
An element A belongs to 14th group and occupies period number 6. A
reacts with conc. HCl. to give B an acid. A is used to prepare C which is used
as an antiknock in automobiles. Identify the element A and the compounds B
and C Write the reactions.
Solution
1.
2.
H2PbCl4 + H2
Arsenic is also used to make pesticides and semi conductors, such as GeAs.
The natural abundance of As, Sb and Bi in the earths crust is relatively low.
69
General trends
Electronic configuration: All these elements have general electronic
configuration of ns2 np3.
Table 3.3 Electronic configuration of group 15 elements
Element
Atomic
Number
Electronic Configuration
Group
Number
Period
Periodic
Number
Number
Nitrogen
15
Phosphorus
15
15
Arsenic
33
15
Antimony
51
15
Bismuth
83
15
Halides of Phosphorus
Phosphorus combines with all the halogens forming phosphorus halides which
are all covalent compounds. Phosphorus chlorides are more important. Tri and
pentachlorides of phosphorus are most common.
I.
4PCl3
Dry white phosphorus is placed in the retort and gently heated on a water bath.
A current of pure, dry chlorine is led over the phosphorus. The phosphorus
trichloride formed being volatile distils over and is collected in a water cooled
receiver.
70
D R Y C H L O R IN E
O
C aC l 2
W H IT E
P H O S PH O R U S
S A N D BATH
P C l3
Chemical Properties
1. It is violently hydrolysed by water giving phosphorus acid and hydrochloric
acid gas.
PCl3 + 3 H2O 3HCl + H3PO3
In a similar manner it reacts with organic compounds containing hydroxyl (OH)
group, such as acids and alcohols.
PCl3 + 3CH3COOH
Acetic Acid
PCl3 + 3C2H5OH
Ethyl alcohol
2.
3CH3COCl + H3PO3
Acetyl Chloride
3 C2H5Cl + H3PO3
Ethyl Chloride
71
PCl3 + Cl2
PCl5
4.
Structure: PCl3 molecule has a pyramidal shape, which arises from sp3
hybridisation of phosphorus atom. One of the tetrahedral positions is occupied
by a lone pair of electrons.
P
Cl
Cl
Cl
Cl
xx
x Px
x
Cl
Cl
x - E lectro n o f p
- E lectro n o f C l
Chemical properties
1.
2.
PCl3 + Cl2
insufficient water
PCl5 + H2O
POCl3 + 2HCl
Excess of water
PCl5 + 4H2O
3.
4.
H3PO4 + 5HCl
Structure
PCl5 molecule has trigonal bipyramidal shape in vapour state which arises
from sp3d hybridisation of phosphorus atom.
Cl
Cl
Cl
x
x
Cl
Cl
x
P
x
Cl
Cl
Cl
x - E lectro n o f p
- E lectro n o f C l
Cl
Cl
b)
Oxides of phosphorus
I.
Physical properties
1. It is a white waxy substance
2. It has a garlic odour.
Chemical properties
1. It reacts with cold water, gives phosphorus acid.
P2O3 +3H2O 2H3PO3
73
2.
H2SO4
SO3
- H2O
P4O10
2HNO3
N2O5
- H2O
P4O10
RCONH2
Amide
-H2O
RCN
Nitrile
c)
Oxy-Acids of Phosphorus
I.
NaH2PO3 + H2O
Sodium dihydrogen Phosphite
Na2HPO3 + 2H2O
Disodium hydrogen Phosphite
O
x x
H
P
x
H
x - E lectro n o f P
- E lectro n o f C l
- E lectro n o f H
HO
OH
H
2H3PO4
2. Laboratory preparation: In the laboratory orthophosphoric acid can be
prepared by boiling a mixture of red phosphorus with 50% nitric acid in a flask
fitted with a reflux condenser on a water bath till no more oxides of nitrogen are
liberated.
Iodine acts as a catalyst. The product is evaporated below 453 K and then
cooled in a vaccum desiccator surrounded by freezing mixture when crystals of
orthophosphoric acid are deposited.
P+5HNO3 H3PO4 +5NO2 +H2O
Physical properties
1. It is a deliquescent crystalline solid.
2. It is soluble in water.
Chemical properties
1. It is a tribasic acid. It combines with alkalies like NaOH to form three series
of salts.
H3PO4 +NaOH
NaH2PO4 + H2O
Sodium Di hydrogen Phosphate
H3PO4 +2NaOH
Na2HPO4
+ 2H2O
Disodium hydrogen Phosphate
H3PO4 + 3NaOH
Na3PO4
+ 3H2O
Sodium Phosphate
H3PO4
3.
589K
H4 P2O7
2HPO3 + H2O
Uses
1.
2.
3.
4.
Structure
Being a tribasic acid, the structure of phosphoric acid is represented as
O
O
x x
O x P x O
x
O
x - E lectro n o f P
- E lectro n o f O
- E lectro n o f H
HO
OH
OH
2.
2PO3 + H2O
77
x P
x
O
O
x x
x
O x
d)
P
x
O
HO
OH
OH
OH
Phosphine - PH3
Phosphine is the best known hydride of phosphorus.
PH3 + 3NaH2PO2
Sodium hypophosphite
723 K
P4 + 6H2
P4O10 + 6H2O
78
PCl3 + 3HCl
PH3 + 4Cl2
PCl5 + 3HCl
Smoke screens
+ 3Ca(OH)2
Problem
An element A occupies group number 15 and period number 3 reacts
with chlorine to give B which further reacts with chlorine to give C at 273 K.
Both B and C are chlorinating agent for organic compounds. C is a better
chlorinating agent because it chlorinates metals also. B reacts with SO3 and
reduces it to SO2. B has a pyramidal shape. C has trigonal bipyramidal shape by
sp3d hybridisation. Identify the element A and the compounds B and C. Write
the reactions.
1.
4PCl3
2.
PCl3 further reacts with Cl2 to give PCl5. Therefore, the compound C is
phosphorus pentachloride and it has a trigonal bipyramidal shape.
PCl3 + Cl2
3.
PCl5
PCl3 and PCl5 are chlorinating agents for organic compounds. So, both
reacts with C2H5OH gives C2H5Cl.
PCl3 + 3C2H5OH
PCl5 + C2H5OH
4.
5.
3C2H5Cl+ H3PO3
C2H5Cl + POCl3 + HCl
2CuCl + PCl3
POCl3 + SO2
Sulphur is less abundant and occurs in free and combined states. Sulphur is
also known as Brim stone.
Atomic
Number
Electronic Configuration
Group
Number
Period
Periodic
Number
Numbe
Oxygen
[He] 2s22p4
16
Sulphur
16
[Ne] 3s23p4
16
Selenium
34
16
Tellurium
52
16
Polonium
84
16
Atomic
Number
Electronic Configuration
Group
Number
Period
Periodic
Number
Numbe
Fluorine
[He] 2s22p5
17
Chlorine
17
[Ne] 3s23p5
17
Bromine
35
17
Iodine
53
17
Astatine
85
17
81
Chemical Properties
1. Oxidising power: An important feature of the halogen is their oxidising
property which is due to high electron affinity of halogen atoms. The oxidising
power decreases from fluorine to iodine. Fluorine is the strongest oxidising agent.
It oxidises other halide ions to halogens in solution or when dry.
F + 2 X 2F + X (X = Cl , Br , I)
2
Halogen of low atomic number oxidises the halide ion of higher atomic number.
2. Solubility: Halogens, being non-polar molecules, do not dissolve to a
considerable extent in a polar solvent like water. However, fluorine reacts with
water readily forming a mixture of O2 and O3.
2F2 + 2H2O
4HF + O2
3F2 + 3H2O
6HF + O3
Chlorine, bromine and Iodine are more soluble in organic solvents such as
CCl4, CHCl3 and produce yellow, brown and violet colour.
3.
i)
All halogens react with hydrogen to form volatile covalent hydrides of formula
HX.
ii)
iii)
Except HF, all hydrogen halides are gases. HF is a liquid because of inter
molecular hydrogen bonding.
H F ....... H F ....... HF ....... HF
82
Fluorine is the most reactive element among halogen. This is due to the
minimum value of FF bond dissociation energy.
2.
Fluorine decomposes cold dilute alkalies liberating OF2 and with conc. alkali,
O2 is liberated. Under similar conditions, the other halogens will give rise to
the hypohalites and halates respectively.
3.
4.
It differs markedly from the other halogens in that it can form two types of
salts with metals. NaF and NaHF2.
5.
The salts of HF differ from the corresponding salts of other hydracids. AgF
is soluble in water while the other AgX are insoluble.
6.
7.
8.
Fluorine, because of the absence of d-orbitals in its valence shell does not
form any polyhalides. Thus we have 3 , Br3, Cl3 ions but no F3 ion.
ETCHING ON GLASS
Etching glass
Industrially, hydrogen fluoride is obtained by heating fluorspar (CaF2) with
concentrated H2SO4 in a lead vessel.
CaF2 + H2SO4 CaSO4 + 2HF.
HF distils over and the vapours are condensed in water in a lead receiver.
Aqueous HF thus obtained is stored in wax bottles. It cannot be stored in glass
or silica bottles as it attacks silicates and silica.
Na2 SiO3 + 6HF Na2SiF6 + 3H2O
SiO2 + 4HF
SiF4 + 2H2O
83
The action of hydrofluoric acid on silica and silicates is used for etching
glass. The glass article is first covered with a film on wax. The design to be
etched is now drawn on the waxed surface and is then exposed to the action of
hydrofluoric acid. Now the glass can be very soon etched. The wax is finally
washed off with turpentine.
3.5.1 ISOLATION OF FLUORINE
Symbol - F Atomic number -9
Period Number
: 2
Valency 1
Group Number
: 17
Atomic mass19
Fluorine does not occur free in nature. It occurs in the combined form.
Dennis Method: This was devised by Dennis, Veeder and Rochow in 1931.
In this fluorine is prepared by the electrolysis of fused sodium or potassium
hydrogen fluoride (perfectly dry) Electrolysis is carried out between graphite
electrodes in a V-shaped electrically heated copper tube. The ends of the tube
are covered with copper caps into which the graphite electrodes are fixed with
bakelite cement. The copper tube is thickly lagged to prevent loss of heat.
KHF2
KF + HF
HF H+ + F
2H+ + 2e H 2
2F 2e F
(At cathode)
(At anode)
B A K E L IT E
ST O PP ER S
H2
N aF
E L EC T R IC
R E SISTA N C E
FU R N A C E
N aF
G R A PH IT E
E L EC T R O D E
C O PPE R U -T U B E S
FU SE D
KH F2
Chemical Properties
Fluorine is the most active member of halogen family.
1. Action with Hydrogen: Hydrogen explodes violently in fluorine even in
the dark.
H2 + F2 2HF
2. Action with non-metals: Non-metals like carbon, silicon and phosphorus
burn in fluorine forming fluorides.
C + 2F2 CF4
Tetra fluoromethane
Si + 2F2 SiF4
Silicon tetrafluoride
2P + 5F2 2PF5
Phosphorus pentafluoride
3.
Uses
1. Fluorine is used in the manufacture of a series of compounds known as
freons. These non-toxic, non-combustible and volatile liquids are used as
refrigerants in refrigerators, deep freezers and air conditioners. The most
common, freon is known as dichlorodifluoro methane CF2 Cl2.
2. CaF2 is used as flux in metallurgy.
3. NaF is used as a preservative to prevent fermentation and also for preventing
dental cavities.
4. SF6 is used as an insulating material in high voltage equipment.
5. Teflon is used as container to store hydrofluoric acid.
6. UF6 is used in the separation of U235 from U238.
INTERHALOGEN COMPOUNDS OR INTERHALOGENS
Each halogen combines with another halogen to form several compounds
known as interhalogen compounds. The less electronegative element is written
first. In naming also, the less electronegative element is mentioned first.
They are divided into four types.
AX
AX3
AX5
AX7
CIF
BrF
BrCl
ICl
IBr
ClF3
BrF3
ICl3
BrF5
IF5
IF7
573K
573K
F7 (AX7 Type)
5F + BrO3 + 3 H+
Bromate
Cl + OH
Cl + O + H+
hypoiodite
Linear Molecule
AX
Although the spatial arrangement of the four electron pairs (bp = 1 and
lps = 3) round the central chlorine atom is tetrahedral, due to the presence of
three lone pairs of electrons in three hybrid orbitals, the shape of AX molecule
gets distorted and become linear.
2. Type AX3 Compounds of the type AX3 have trigonal bipyramidal structure,
Fig. 3.5 for the ClF3 molecule.
Bipyramidal structure arises out of sp3d hybridisation involved in the formation
of this compound, as illustrated in the Fig.3.6. The three dotted arrows indicate
electrons contributed by the three fluorine atoms (without lone pair it is T-shaped).
88
F
I
F
F
F
Fig. 3.8 Structure of IF7
Problem
An element A occupies group number 17 and period number 2, shows
anomalous behaviour. A reacts with water forms a mixture of B, C and acid D.
B and C are allotropes. A also reacts with hydrogen violently even in dark to
give an acid D. Identify A,B,C and D. write the reactions.
Solution
i) The element A that occupies group number 17 and period number 2 is
fluorine.
ii) Fluorine reacts with water and forms a mixture of B and C
2F2 + 2H2O 4HF + O2
89
3F2 + 3H2O
6HF + O3
Atomic
Number
Electronic Configuration
Group
Number
Period
Periodic
Number
Numbe
Helium
1s2
18
Neon
10
1s22s22p6
18
Argon
18
1s22s22p63s2 3p6
18
Krypton
36
1s22s22p63s23p63d104s2 4p6
18
Xenon
54
1s22s22p63s23p63d104s2
4p64d105s2 5p6
18
Radon
86
1s22s22p63s23p63d104s2 4p6
4d104f145s2 5p65d106s2 6p6
18
90
2 NO
2 NO + O2 2NO2
2NO2 + 2NaOH NaNO3 + NaNO2 + H2O
Oxygen if any is removed by introducing alkaline pyrogallol in the globe.
The supply of air and electric discharge is shut after some time and the remaining
mixture of noble gases is pumped out.
91
To Tr a n sfo rm e r
Soda out
G a se s in
S o d a in
krypton and xenon are adsorbed by the charcoal while helium and neon remain
unadsorbed. These are pumped out and collected.
The mixture of helium and neon is kept in contact with coconut charcoal at
93K which completely adsorbs neon leaving free helium.
The charcoal at 173K containing argon, krypton and xenon is placed in
contact with another charcoal at the temperature of the liquid air when argon
diffuse into the other charcoal.
The temperature of the first charcoal (temp.173K) still containing krypton
and xenon is raised to 183K when krypton is set free while xenon remain adsorbed
in the charcoal. When it is heated, xenon is recovered.
XENON FLUORIDE COMPOUNDS
Xenon forms three binary Fluorides XeF2, XeF4, and XeF6 by the direct
union of elements under appropriate experimental conditions.
Xe+F2
673K
XeF2
673K
Xe + 2 F2
XeF4
573K
Xe+ 3 F2
XeF6
93
SELF EVALUATION
A. Choose the correct answer
1
2.
b) Si
6.
c) P2 O3
d) SO3
b) P2O5
c) H3PO3
d) H3PO4
b) trigonal bipyramidal
c) linear
d) tetrahedral
c) PH3
d) H3PO3
c) chlorine
d) iodine
9.
b) NO2
a) pyramidal
a) fluorine
8.
d) Sn
a) PCl3
7.
c) Ge
5.
d) In
An element which was burnt in limited supply of air to give oxide A which
on treatment with water gives an acid. B. Acid B on heating gives acid C
which gives yellow precipitate with AgNO3 solution A is
a) SO2
4.
c) Ge
3.
b) Al
b) HF
c) HBr
d) HCl
b) HCl
c) HBr
d) HI
b) 15
c) 17
95
d) 18
b) XeF4
c) XeO3
d) ArF6
b) H2
c) N2
d) Ar
b) Ne
c) Ar
d) Kr.
96
b) P2O5
c) PCl3
d) PCl5 e) PH3
31. How fluorine is isolated from their fluorides? Describe its important properties
and uses.
32. Give a detailed account of the interhalogen compounds with special reference
to the compounds involving iodine. Draw their structures.
33. Describe in detail how noble gases are isolated from air?
34. Give an account of various types of compounds which are formed by xenon?
D. Practice Problems
1.
2.
3.
4.
Group 18 is known as rare gases or inert gases, with closed valence shell
electronic configuration exhibit low chemical reactivity. Xenon can form
compounds with fluorine.
References
1.
2.
3.
4.
98
4. d - BLOCK ELEMENTS
Learning Objectives
( To study the nature of four transition series and their general
characteristic properties of d-block elements.
(To learn the general methods of extraction of metals.
( To have an idea about the composition, properties and uses of alloys.
( To study about the methods of preparation of compounds, their
properties and uses.
There will come a time, when the world will be filled with one science, one
truth, one industry, one brotherhood, one friendship with nature... this is my
belief, it progresses, it grows stronger, this is worth living for, this is worth
waiting for.
Dimitry Mendeleyev, Russian Chemist in YA Urmantsev.
99
27
Co
40
Zr
46
Pd
110
Uun
The d-block elements are located in the middle of the periodic table and
consists of metals only. It consists of four series, each series consists of 10 elements.
In these elements, the last electron enters the d orbital of the penultimate
shell i.e. the last electron goes to (n-1) d orbital. Hence these elements are named
as d-block elements. These elements have partly filled d-subshells in their
elementary form or in their simple ions. The d-block elements are called transition
elements because these represent a transition from highly electropositive elements
(metals) of s-block to least electropositive elements (non-metals) of p-block.
Classification of d-block Elements
Based on whether the last electron goes to 3d,4d,5d or 6d orbital, d-block
elements are classified into four series. They are
i)
100
Sc
Ti
Cr
Mn
Fe
Co
Ni
Cu
Zn
144
132
122
118
117
117
116
115
117
125
102
It may be noted that Zinc, Cadmium and Mercury salts do not form any
coloured compounds because of the absence of vacant d orbitals to which electrons
can be excited. Sc3+ ions are also colourless because of the absence of d-electrons.
4.1.4 Catalytic Properties
Most of the transition metals and their compounds are used as catalyst.
The catalytic activity of transition metals is due to the following reasons.
i)
They show a variety of oxidation states and thereby can form intermediate
products with various reactants.
ii) They are also capable of forming interstitial compounds which can adsorb
and activate the reacting species.
Some examples of catalyst are
i)
ii)
The energies of (n 1)d and ns orbitals are fairly close to each other.
The elements which exhibit the maximum number of oxidation states occur
either in or near the middle of the series. For example , in the first transition
series manganese exhibits maximum number of oxidation states (+2 to +7).
2.
The elements in the beginning of the series exhibit fewer oxidation states
because they have less number of d-electrons which they can lose or
contribute for sharing. The elements at the end of the series exhibit fewer
oxidation states, because they have too many d electrons and hence fewer
vacant d-orbitals can be involved in bonding.
103
3.
The transition elements in lower oxidation states (+2 and +3) generally form
ionic bonds and in higher oxidation state form covalent bonds.
4.
The highest oxidation state shown by any transition metal is +8. For example,
ruthenium and osmium show highest oxidation states of +8 in some of their
compounds.
5.
Paramagnetic substances
Diamagnetic Substances
= 1(1 + 2)BM =
3 = 1.732 B.M
104
Larger the value of magnetic moment, the greater is the paramagnetic character.
In addition to paramagnetic and diamagnetic substance, there are a few
substances such as iron which are highly magnetic as compared to ordinary metals.
These substances are called ferromagnetic substances
4.1.7 Complex formation
The cations of d-block elements have strong tendency to form complexes
with certain molecules (e.g. CO, NO, NH3....etc) or ions (e.g. F-, Cl-, CN....etc) called ligands. Their tendency to form complexes is due to two reasons.
i)
ii)
Ores
i)
ii)
iii)
2.
Roasting
Moisture is removed.
The volatile impurities are removed.
Sulphur, phosphorus, arsenic and antimony which are present as impurity
are removed as volatile oxides.
S + O2
P4 + 5O2
4As + 3O2
SO 2
2P 2O5
2As2O3
iv) The copper pyrite is partly converted into sulphides of copper and iron.
2CuFeS2 + O2
2FeS + 3O2
3.
Smelting
The roasted ore is mixed with powdered coke and sand and is heated in a
blast furnace. It is made of steel plates lined inside with fire clay bricks. Hot air at
800C is introduced from the tuyers near the base of the furnace. As a result, the
following changes occur.
2FeS + 3O2
2FeO + 2SO2
106
FeO
2Cu2S
Cu2O
FeO
+
+
+
+
SiO2
3O2
FeS
SiO2
As a result of smelting, two separate molten layers are formed at the bottom of
the furnace. The upper layer consists of slag and is removed as a waste while the
lower layer is called matte. It chiefly consists of cuprous sulphide and some
unchanged ferrous sulphide.
4.
Bessemerisation
2FeO + 2SO2
FeSiO3 (slag)
2Cu2O
6Cu
+ 2SO 2
+ SO 2
Refining
When electric current is passed through the electrolytic solution pure copper get
deposited on the cathode ,impurities settle near the anode in the form of sludge
called anode mud.
Properties
Physical properties
Copper is a reddish brown metal, with high lustre, high density and high
melting point 1356C.
Chemical Properties
i) Action of air and moisture
Copper gets covered with a green layer of basic copper carbonate, in the
presence of CO2 and moisture
2Cu + O2 + CO2 + H2O
ii)
Cu(OH)2 . CuCO3
(Green) Copper Carbonate
Action of Heat
1370 K
Below
1370 K
4Cu + O2 Above
2CuO
2Cu2O
Dilute acids such as HCl and H2SO4 have no action on these metals in the
absence of air or an oxidising agent. Copper dissolves in these acids in the
presence of air
2Cu + 4HCl + O2 (air)
b)
2CuCl2 + 2H2O
c)
Cu + 2H2SO4 (con)
CuCl2
Action of alkalis
Copper is not attacked by alkalies.
Uses
1.
2.
3.
4.
It is extensively used for making electric cables and other electric appliances.
It is used for making utensils, containers, calorimeters, coins, ...... etc.
It is used in electroplating.
It is alloyed with gold and silver for making coins and jewellery.
Alloys of Copper
Alloy
% composition
Uses
i)
Brass
ii)
Bronze
iii)
109
: 51.99
Valency : 0,1,2,3,4,5,6
Atomic number : 24
Symbol : Cr
Position in the periodic table : Period Number -4, Group Number -6.
L.N. Vanquelin, a french chemist discovered a new element in 1797, while
examining a mineral found in Siberia. It was named chromium because it forms
coloured compounds [Greek word - chroma - colour]
Occurrence
Metallic chromium does not occur in the native state. In India chromite ore
occurs in Bihar, Mysore, Chennai and Bombay.
Ores
The important ore of chromium is
Chromite or chrome ore, FeO Cr2O3
The chief ore of chromium is chromite ore.
Extraction of chromium metal from chromite ore
The extraction of chromium metal from chromite ore consists of the following
steps.
1.
Concentration
The crushed ore is concentrated by gravity separation method.
2.
The concentrated ore is mixed with excess of Na2CO3 and a small amount
of lime and roasted in a reverberatory furnace at 900-1000C in the presence
of free supply of air. During this process, chromite ore is converted into soluble
sodium chromate.
110
Chromite ore
Na2Cr2O4 + 3CO
Na2Cr2O4 + H2O
Cr2O3 + 2 NaOH
Na2Cr2O7 + 3C
3. Magnesium ribbon,
5. Cr2O3 + Al
Chromic oxide is mixed with powdered Aluminium in the ratio 3:1 and is
placed in a large fire clay crucible. A mixture of barium peroxide and Mg powder
is placed over this. The crucible is surrounded by sand which prevents loss of
heat by radiation. The mixture is ignited by a piece of Mg ribbon. During this
process a large amount of heat is liberated, in which Cr2O3 is reduced to chromium.
111
The molten chromium is collected in the crucible and aluminium oxide is removed
as slag.
Cr2O3 + 2Al 2Cr + Al2O3 + 468.6 kJ
Properties of Cr
Physical Properties
1.
2.
3.
It melts at 2113K.
Chemical Properties
1.
The articles to be plated with chromium are made the cathode in an electrolytic
bath consisting of chromic acid and sulphuric acid while the anode is made
of a plate of lead. During electrolysis chromium deposits on the article
(cathode). Generally the articles are first plated with nickel and then subjected
to chromium plating.
2.
3.
4.
5.
Alloys of chromium
Alloy
% composition
i)
Ferrochrome
Cr = 65% Fe = 35%
It is used in manufacture of
chrome steel, burglar proof safe
ii)
Stainless steel
Cr = 11-13%
C = 0.1 - 0.4%
Fe = 73% Ni = 8%
iii)
Nichrome
Cr = 15%, Ni = 60%
Fe = 25%
Cr = 20-35%
Co = 40-80%
Ni = 0.25%
C = 0.75 - 2.5%
iv) Stellite
113
Uses
The chief ore of Zinc is Zinc blende. In India large deposits of zinc blende occur
in Zawar mines near Udaipur in Rajasthan.
Extraction of Zinc from Zinc blende
The extraction of Zinc from Zinc blende involves the following steps.
1. Concentration
The ore is crushed and then concentrated by froth-floatation process.
2. Roasting
The concentrated ore is then roasted in the presence of excess of air at
about 1200 K.
+ 2SO2
Reduction
Zinc oxide is mixed with powdered coke and heated to 1673 K in a fire
clay retort, in which ZnO is reduced to zinc metal.
114
ZnO + C 1673
K
Zn + CO
Purification
Zinc is purified by electrolytic refining. In this process, Impure Zinc is anode
and cathode is of pure thin sheet of Zinc. The electrolyte is ZnSO4 solution
containing a little of dil.H2SO4. On passing electric current, pure zinc get deposited
at the cathode.
Properties
Physical properties
i)
ii)
iii)
Chemical properties
i)
Action of air
When heated in air at 773 K, it burns to form a white cloud of Zinc oxide
which settles to form a wooly flock called philosophers wool.
773 K
2Zn + O2
2ZnO
ii)
Action of water
Pure zinc does not react with water but impure zinc (Zn-Cu couple)
decomposes steam quite readily evolving H2 gas.
Zn + H2O (steam) ZnO + H2
iii) Action of dilute acids
Pure zinc is not attacked by dilute acids. However, impure zinc reacts with
dilute acids with the liberation of H2.
Zn + 2HCl
Zn + H2SO4
ZnCl2 + H2
ZnSO4 + H2
v)
Action of HNO3
(about 1%). Silver is obtained to a small extent from the gold ores in the kolar
fields in Karnataka and in the Anantapur mines.
Extraction of silver from the Argentite ore
Silver is extracted from the argentite ore by the Mac-Arthur and Forrests
cyanide process. The various steps involved in this process are as follows.
1.
Concentration
The crushed ore is concentrated by froth-floatation process.
2.
3.
Electrolytic refining
The impure silver is further purified by electrolytic refining. The impure silver
is made the anode while a thin sheet of pure silver act as the cathode. The
electrolyte is silvernitrate acidified with 1% nitric acid. On passing electricity
pure silver gets deposited at the cathode.
5.
Silver coins are Ag-Cu alloys. Ag can be obtained from such an allloy by
dissolving the alloy in concentrated HNO3, a solution containing mixture of AgNO3
and Cu(NO3)2 is obtained. The solution is boiled to expel excess of nitric acid,
then the solution is treated with con.HCl, silver is precipitated as AgCl. AgCl is
separated and converted to silver by fusing with excess Na2CO3.
4AgCl + 2Na2CO3 4Ag + 4NaCl + 2CO2 + O2
117
The silver thus obtained, is purified by fusion with borax and followed by
electrolytic purification.
Properties
Physical properties
i)
ii)
iii) Molten silver absorbs about twenty times its volume of oxygen which it
again expels on cooling. Globules of molten silver are thrown off. This is called
spitting of silver. This can be prevented by covering the molten metal with a
layer of charcoal.
Chemical properties
i)
ii)
Hot con.HNO3 or con.H2SO4 react with silver liberating NO2 and SO2
respectively.
Ag + 2 HNO3 AgNO3 + NO2 + H2O
2Ag + 2H2SO4 Ag2SO4 + SO2 + 2H2O
iii) Action with chlorine
Chlorine attacks silver, forming silver chloride.
2Ag + Cl2 2AgCl
iv) Action of alkalies
Silver is not attacked by alkalies.
Uses of silver
i)
ii)
iii)
The gold ore is crushed and powdered, and then concentrated by frothfloatation process.
ii)
Roasting
119
Gold is a lustrous yellow metal which melts at 1063C to a green liquid and
boils at 2610C.
ii)
iii)
Chemical properties
i)
ii)
Fineness of gold
Gold content of an alloy of gold is termed its fineness and is generally
expressed in carats. Pure gold is 24 carats. Ornaments available these days are
made of 18 carat gold, which is an alloy containing 18 parts by weight of gold
alloyed with 6 parts by weight of another metal generally copper.
4.5 COMPOUNDS
4.5.1 Potassium dichromate (K2Cr2O7)
Preparation of potassium dichromate from chrome iron ore
The preparation of K2Cr2O7 from its ore involves the following steps
i)
The powdered ore is mixed with Na2CO3 and quick lime, then roasted in a
reverberatory furnace with free expose to air.
4FeO.Cr2O3 + 8Na2CO3 + 7O2 8Na2CrO4 + 2Fe2O3 + 8CO2
ii)
K2Cr2O7 + 2NaCl
Properties
Physical properties
1.
2.
Chemical properties
1.
Action of Heat
With Alkalies
2CrO42- + 2H+
Yellow
Oxidising properties
K2Cr2O7 is a powerful oxidising agent. In presence of dil.H2SO4, one mole
122
It liberates I2 from KI
K2Cr2O7 + 7H2SO4 + 6KI 4 K2SO4 + Cr2 (SO4)3 + 3 I2 + 7H2O
ii)
When salt containing chloride is treated with K2Cr2O7 and con. H2SO4
reddish brown vapours of chromyl chloride are obtained.
K2Cr2O7 + 4KCl + 6H2SO4 2CrO2Cl2 + 6 KHSO4 + 3H2O
Chromylchloride
This reaction is used in the detection of chloride ions in qualitative analysis.
Uses
i)
ii)
iii)
iv)
Properties
Physical properties
1.
2.
The anhydrous salt is colourless but the hydrated salt is blue in colour.
It readily dissolves in water but is insoluble in alcohol.
Chemical Properties
1.
Action of Heat
SO 3 + CuO
2.
1 0 0 C
-4 H 2 O
7 2 0 C
C u S O 4 .H 2 O
-H 2 O 2 3 0 C
CuSO 4
(W h ite)
Action of ammonia
Copper sulphate gives deep blue colour with NH4OH forming complex
compound.
CuSO4 + 4NH4OH [Cu (NH3)4]SO4 + 4H2O
3.
Action of KI
Action of alkalies
With alkalies, a pale blue precipitate of copper hydroxide is formed.
CuSO4 + 2NaOH Cu(OH)2 + Na2SO4
Pale blue precipitate
6.
Uses
1.
2.
3.
It is soluble in water.
Its aqueous solution may decompose on exposure to light.
Chemical Properties
1.
Action of Heat
On heating AgNO3 decomposes in two stages
125
2A gN O 3
A gN O 2
2.
723 K
980 K
2A gN O 2 + O 2
S ilv er n itrite
Ag
+ NO2
With NaCl
AgNO3 gives white precipitate of AgCl with soluble ionic chlorides.
AgNO3 + NaCl AgCl + NaNO3
3.
4.
AgNO3 gives pale yellow precipitate of AgBr with bromides and yellow
AgI with iodides.
AgNO3 + KBr AgBr + KNO3
Yellow ppt
AgNO3 + KI AgI + KNO3
Yellow ppt
5.
126
Action of Heat
ZnO + CO 2
Uses
i)
ii)
iii)
SELF EVALUATION
A. Choose the correct answer
1. The general electronic configuration of d-block elements is
a) (n-1)d1-10 ns0-2
b) (n-1) d1-5 ns2
c) (n-1)d0 ns1
d) None of these
2. Formation of coloured ions is possible when compounds contains
a) paired electrons
b) unpaired electrons
c) lone pairs of electrons
d) none of the above
3. Paramagnetism is common in
a) p-block elements
b) d-block elements
c) s-block elements
d) f-block elements
3+
4. The colour of Ti(H2O)6 ion is due
a) d-d transistion
b) Presence of water molecules
c) Inter atomic transfer of electrons
d) None of the above
5. The electronic configuration of chromium is
a) 3d6 4s0
b) 3d5 4s1
b) 3d4 4s2
d) 3d3 4s2 4p1
6. Paramagnetism is the property of
a) paired electrons
b) completely filled electronic subshells
c) unpaired electrons
d) completely vacant electronic subshells
7. d-block elements form coloured ions because
a) They absorb some energy for d-s transition
b) They absorb some energy for p-d transition
c) They absorb some energy for d-d transition
d) They do not absorb any energy
8. The correct electronic configuration of copper atom is
a) 3d10 4s1
b) 3d10 4s2
c) 3d9 4s2
d) 3d5 4s2 4p4
9. Copper is extracted from
a) cuprite
b) copper glance
c) malachite
d) copper pyrites
128
129
a)
n(n 1)
b)
n(n + 1)
c)
n(n + 2)
d)
n(n + 1)(n + 2)
B 373K
C 423K
D
A 305K
2.
132
5. f - BLOCK ELEMENTS
Learning Objectives
( To learn the general characteristics of f-block elements and extraction.
( To study the comparison of properties of Lanthanides and Actinides
( To know the general method of extraction of Lanthanides.
( To recognise the uses of Lanthanides and Actinides.
133
d -B L O C K
T R A N S IT IO N E L E M E N T S
1 3 -1 7
p -B L O C K
1 8 in ert g ases
1 -2 s-B L O C K
3 -1 2
f- Block
INNER TRANSITION ELEMENTS
Basicity of ions
Due to lanthanide contraction, the size of Ln3+ ions decreases regularly with
increase in atomic number. According to Fajans rule, decrease in size of
Ln3+ ions increase the covalent character and decreases the basic character
between Ln3+ and OH- ion in Ln(OH)3. Since the order of size of Ln3+ ions
are
La3+ > Ce3+ ............... >Lu3+
135
ii)
iii)
Oxidation states
These elements shows the oxidation states of +2, +3, +4, +5 and +6. Out
of these, +4 oxidation state is most common state.
3.
136
H 2 PO 4 )
137
Actinide s
i)
Binding energies of 4f
electrons are higher.
i)
ii)
ii)
iii)
iii)
iv)
iv)
v)
v)
vi)
vi)
vii)
vii)
viii)
2.
Ceria (CeO2) and thoria (ThO2) are used in gas lamp materials.
138
3.
Cerium salts are used in dyeing cotton, lead storage batteries and as catalyst.
4.
5.
Uses of Actinides
1.
2.
2.
b)
d)
4.
b)
c)
3.
b) +1
c)
139
+3
d)
+4
5.
6.
The elements in which the extra electron enters (n-2)f orbitals are called
a)
c)
7.
c) Magnetite d) Cassiterite
s block elements
d block elements
b)
d)
p block elements
f block elements
8.
Ceria is used in
a) toys
9.
b) CeO2
c) N 2O 5
d) Fe2O3
d) Actinides
b) Lanthanido-thermic process
d) Oxidation process
b) +2
c) +3
d) Alkalimetals
d) +4
b) Steam distillation
d) Sublimation
16. What is the difference in the electronic configuration of transition and innertransition elements?
17. What are lanthanides? Give the various oxidation states of lanthanides.
18. What are mish metals? Give their uses.
19. Write the uses of Lanthanides and Actinides.
C. Answer not exceeding 60 words
20. What is lanthanide contraction? Discuss its causes and consequences.
21. Account for the following.
i) +3 oxidation state of lanthanides is the most stable.
ii) A few 4f elements show +2 or +4 oxidation states in addition to the
characteristic oxidation state of +3.
iii) Lanthanides are grouped together.
22. Comparing La(OH)3 and Lu(OH)3, which is more basic and explain why?
23. Discuss the position of lanthanides in the periodic table.
24. Describe the extraction of Lanthanides from monozite sand.
Summary
The elements in which the extra electron enters (n-2) f orbitals are called
f-block elements. These elements are also called as inner transition elements.
The two series of f-block elements are lanthanide series and Actinide series. The
general properties of lanthanides and electronic configuration, oxidation states
radii of tripositive ions are discussed. Cause and consequences of lanthanide
contraction are discussed. General properties of actinide elements are given. A
flow chart is given for extraction of lanthanides from monazite sand. Similarities
and differences between lanthanides and actinides are tabulated.
References
1)
2)
6.1 INTRODUCTION
A salt is formed by the neutralisation of an acid by a base. There are different
types of salts. They are:-
a)
a) Simple salt
b) Molecular (or) addition compounds
Simple salt
A simple salt is formed by the neutralisation of an acid by a base.
KOH
+ HCl
KCl + H2O
Normally, a simple salt ionises in water and produces ions in solution. The
solution of the simple salt exhibits the properties of its component ions.
b)
i)
Double salts
- Potash alum
- Mohrs salt
Ferrous cyanide
Fe(CN)2 . 4KCN
In K4 [Fe (CN)6] the individual components lose their identity. The metal of
the complex ion is not free in solution unlike metal in double salt in solution.
Nature of coordination (or) complex compounds
i)
ii)
iii)
4K+
+
simple cation
[Cr(NH3)6] [Co(CN)6]
..N H - C H - C H - ..N H
2
145
Neutral ligands
The neutral ligands are named as such without any special name. But water
is written as aqua : Ammonia is written as ammine. Note that two ms to
distinguish from organic amine
CO-Carbonyl, NO-Nitrosyl, NH2 - CH2 - CH2 - NH2-ethylenediamine
(en), Pyridine C5H5N.
Negative Ligands
Negative ligands end in suffix O.
Example
F --Fluoro, Cl --Chloro, C 2O 42--Oxalato, CN --Cyano, NO 2--Nitro,
Br - -Bromo, SO 42- -Sulphato, CH 3COO - -acetato CNS -thiocyanato,
NCS--isothiocyanato, S2O32--thiosulphato.
Chelates
If a ligand is capable of forming more than one bond with the central metal
atom (or) ion then the ring structures are produced which are known as metal
chelates. Hence the ring forming group are described as chelating agents (or)
polydentate ligands.
2 N H 2C H 2C H 2N H 2 + C u
H 2C
..N H
..N H
2+
NH2
Cu
2
.. ..
H 2C
+2
NH2
CH2
CH2
Coordination sphere
In a complex compound, it usually, central metal ion and the ligands are
enclosed with in square bracket is called as coordination sphere. This represents
a single constituent unit. The ionisable species are placed outside the square
bracket.
146
[Cu(NH3)4]2+
These ions do not ionise to give the test for constituent ions.
Coordination number
The coordination number of a metal ion in a complex can be defined as the
number of ligand donor atoms to which the metal is directly bonded. Numerically
coordination number represents the total number of the chemical bonds formed
between the central metal ion and the donor atoms of the ligands. For example in
K4[Fe(CN)6] the coordination number of Fe(II) is 6 and in [Cu(NH3)4]SO4 the
coordination number of Cu(II) is 4.
Charge on the complex ion
Charge on the complex ion is equal to the sum of the charges on the metal
ion and their ligands.
Example
1.
2.
Similarly for [Fe(CN)6]4- (or) [Fe2+(CN)6]4The sum of the charge on the metal ion and the ligand = 4.
Charge on the metal ion (Fe2+) = +2
Charge on the ligand (CN-)
= 6 (-1) = 6
147
In naming the entire complex, the name of the cation is given first and the
anion second (just as for sodium chloride), no matter whether the cation or
the anion is the complex species.
2.
In the complex ion, the name of the ligand or ligands precedes that of the
central metal atom (This procedure is reversed for writing formulae).
3.
Ligand names generally end with O if the ligand is negative (chloro for
Cl-, cyano for CN-, hydrido for H-) and unmodified if the ligand is neutral
(methylamine for MeNH2).
Special ligand names are aqua for water, ammine for ammonia, carbonyl
for CO, nitrosyl for NO.
4.
A Greek prefix (mono, di, tri, tetra, penta, hexa, etc.) indicates the number
of each ligand (mono is usually omitted for a single ligand of a given type). If
the name of the ligand itself contains the terms mono, di, tri, like
triphenylphosphine, ligand name is enclosed in parentheses and its number
is given with the alternate prefixes bis, tris, tetrakis instead.
For example, [Ni(PPh3)2Cl2] is named dichlorobis(triphenylphosphine)
nickel(II).
5.
6.
If the complex ion is negative, the name of the metal ends in ate for example,
ferrate, cuprate, nickelate, cobaltate etc.
7.
If more than one ligand is present in the species, then the ligands are named
in alphabetical order regardless of the number of each. For example, NH3
(ammine) would be considered as a ligand and come before Cl- (chloro).
Argentate
Cuprate
Fe
Ni
Ferrate
Nickelate
ii)
tris(ethylenediamine)cobalt(III) chloride
[Co(NH3)3(NO2)3]
triamminetrinitrocobalt (III)
K2[CoCl4]
potassiumtetrachlorocobaltate(II)
A7) Potassiumtris(oxalato)
chromate(III) trihydrate
- pentaamminechlorocobalt(III) ion
[CoIII (NH3)6]Cl3
- Hexaamminecobalt(III) chloride
[CrIII (en)3]Cl3
K4[FeII(CN)6]
- Potassium hexacyanoferrate(II)
[NiII(CN)4]2-
- Tetracyanonickelate(II) ion
[CuII(NH3)4]2+
- Tetraamminecopper(II) ion
[PtII Cl2(NH3)2]
- Diamminedichloroplatinum(II)
149
6.4 ISOMERISM
Compounds having the same chemical formula but different physical and
chemical properties due to the different structural arrangements are called isomers.
This phenomenon is known as isomerism.
Coordination compounds exhibit two major types of isomerism, namely
(A) structural isomerism and (B) stereoisomerism (space isomerism). Each of
these is further classified as shown below.
A) Structural isomerism
a) Coordination isomerism
c) Hydrate or Solvate isomerism
e) Ligand Isomerism
b) Ionisation isomerism
d) Linkage isomerism
B) Stereoisomerism
a) Geometrical isomerism
b) Optical isomerism
2.
b)
Ionisation isomerism
[Co(NH3)5 SO4]Br
pentaamminebromocobalt(III) sulphate
The red-violet isomer yields sulphate ion and the red isomer furnishes bromide
ion in solution.
[Co(NH3)4Cl2]NO2
and
[Co(NH3)4 NO2Cl]Cl
Tetraamminedichlorocobalt(III) nitrite
[Co(NH3)5NO3]SO4
Tetraamminechloronitrocobalt(III) chloride
and
[Co(NH3)5 SO4]NO3
pentaamminenitratocobalt(III) sulphate
c)
pentaamminesulphatocobalt(III) nitrate
The best known examples of this type of isomerism occurs for chromium
chloride CrCl3.6H2O which may contain 4, 5, (or) 6 coordinated water
molecules.
1.
2.
[Cr(H2O)5Cl]Cl2.H2O - grey-green
Pentaaquachlorochromium(III) chloride monohydrate
3.
[Cr(H2O)6]Cl3 - Violet
Hexaaquachromium(III) chloride
These isomers have very different chemical properties and on reaction with
AgNO3 to test for Cl- ions, would find 1,2, and 3 Cl- ions in solution respectively.
d)
Linkage isomerism
e)
Ligand isomerism
Ligand isomerism arises from the presence of ligands which can adopt
different isomeric forms. An example is provided by diaminopropane, which
may have the amine groups in the terminal (1,3-) positions or in the 1,2-positions.
H2N - CH2 - CH2 - CH2 - NH2 or
Geometric isomers are possible for both square planar and octahedral
complexes, but not tetrahedral. In a cis-isomer two identical (or) similar groups
are adjacent to each other whereas in a trans-isomer they are diametrically
opposite to each other.
Square planar complexes of the type [Ma2b2]n+ where a and b are
monodentate ligands, exist as cis and trans-isomers as shown below. Example
of this type of complexes are [Pt (NH3)2 Cl2] and [Pd(NH3)2 (NO2)2]. The cistrans isomers of these compounds are represented as
a
M
b
b
a
tra n s-iso m e r
b
c is-iso m e r
H 3N
NH3
H 3N
Pt
Pt
NH3
Cl
tra n s-iso m e r
Cl
Cl
c is-iso m e r
c is-d ia m m in ed ich lo ro p la tin u m (II)
Cl
152
H 3N
H 3N
NH3
NO2
Pd
Pd
O 2N
NH3
O 2N
tran s-iso m er
NO2
cis-iso m er
cis-d iam m in ed in itro p allad iu m (II)
1
2
5
M
4
6
Along the twelve edges of the octahedron, there are twelve cis positions.
They are (1,2) (1,3) (1,4) (1,5) (2,6) (3,6) (4,6) (5,6) (3,4) (4,5) (2,5) and
(2,3). In order to avoid confusion, generally it is assumed that the 1,2 positions
are cis-positions. There are three trans positions; they are (1,6) (2,4) and (3,5).
Normally it is taken that 1,6 positions are trans-positions in order to avoid
confusion.
An octahedral complex of the type [Ma4b2] where a and b are monodentate
ligands, exists as two geometrical Isomers:
n+
b
a
M
a
n+
b
a
M
a
cis-iso m e r
a
b
tran s-isom er
153
H 2C
H2
N
Cl
Cl
Cl
CH2
NH2
NH2
Co
H 2C
N
H2
CH2
Co
NH2
H 2N
H 2C
CH2
H 2N
NH2
CH2
CH2
Cl
cis-iso m e r
tran s-iso m e r
Cl
py
py
Cl
Rh
Rh
Cl
tran s-iso m er
py
cis-iso m ers
b)
py
py
Cl
py
Cl
Optical Isomerism
that the isomers rotate the plane of polarised light either to the left or right. In a
coordination compound of type [PtCl2(en)2]12+, two geometrical isomers are
possible. They are cis and trans. Among these two isomers, cis isomer shows
optical activity because the whole molecule is asymmetric.
en
en
Cl
lC
Pt
Pt
Cl
lC
en
en
2)
3)
4)
5)
6)
The ligands have unshared pair of electrons. These unshared pair of electrons
are donated to central metal ion or atom in a compound. Such compounds
are called coordination compounds.
Werners representation
Werner represented the first member of the series [Co(NH3)6]Cl3 as follows.
In this representation, the primary valency (dotted lines) are satisfied by the three
chloride ions. The six secondary valencies (solid lines) are satisfied by the six
ammonia molecules.
NH3 Cl
H 3N
Cl
NH3
Co
H 3N
Cl
NH3
NH3
Defects of Werners theory
Werners theory describes the structures of many coordination compounds
successfully. However, it does not explain the magnetic and spectral properties.
6.5.2 Valence bond theory (VB Theory)
Valence bond theory, primarily the work of Linus Pauling regarded bonding
as characterized by the overlap of atomic or hybrid orbitals of individual atoms.
The postulates of valence bond theory
1)
156
2)
These vacant orbitals form covalent bonds with the ligand orbitals.
3)
A covalent bond is formed by the overlap of a vacant metal orbital and filled
ligand orbitals. This complete overlap leads to the formation of a metal
ligand, (sigma) bond.
4)
A strong covalent bond is formed only when the orbitals overlap to the
maximum extent. This maximum overlapping is possible only when the metal
vacant orbitals undergo a process called hybridisation. A hybridised orbital
has a better directional characteristics than an unhybridised one.
The following table gives the coordination number, orbital hybridisation and
spatial geometry of the more important geometrics.
Coordination number
Types of hybridisation
2
4
4
6
6
sp
sp3
dsp2
d2sp3
sp3d2
Geometry
linear
tetrahedral
square planar
octahedral
octahedral
Magnetic moment
A species having atleast one unpaired electron, is said to be paramagnetic.
It is attracted by an external field. The paramagnetic moment is given by the
following spin-only formula.
s = n(n+ 2) BM
s = spin-only magnetic moment
n = number of unpaired electrons
BM = Bohr magneton, the unit which expresses the magnetic moment. When
the species does not contain any unpaired electron, it is diamagnetic.
Number of unpaired electrons
1(1 + 2) = 3 = 1.73
2(2 + 2) = 8 = 2.83
157
3(3 + 2) = 15 = 3.87
4(4 + 2) = 24 = 4.90
5(5 + 2) = 35 = 5.92
Nickel atom
Outer electronic configuration 3d8
3d
4s2
4s
4p
Ni atom
Ni +2 ion
[Ni(NH3)4]2+
N
N
N
N
N
N
N
N
s = 2(2 + 2) = 2.83 BM
Since the hybridisation is sp3, the geometry of the molecule is tetrahedral.
2)
[Ni(CN)4]2-
158
4s
3d
[N i(C N ) 4 ]
2-
N
N
4p
N
N
NN
NN
CN CN CN CN
d sp h y brid isatio n
The geometry of the molecule is square planar.
Octahedral complexes
1)
Fe atom
3d6 4s2
4s
4p
3d
4s
4p
3d
4s
F e ato m
F e + 2 io n
II
[F e (F ) 6 ]
4d
4p
N
N
N
N
F-
N
N
F- F-
N
N
N
N
F-
N
N
F- F-
sp 3 d 2 h y b rid is atio n
s 4(4 + 2) = 24 = 4.90 BM
The molecule is paramagnetic. The geometry of the molecule is octahedral.
2)
Fe+2 ion
4s
3d
4p
In [Fe(CN)6]4- complex the CN- ligand is a powerful ligand, it forces the unpaired
electrons in 3d level to pair up inside. Hence the species has no unpaired electron.
The molecule is diamagnetic.
159
4s
3d
[F e (C N ) 6 ] 4 -
N
N
N
N
N
N
4p
NN
NN
NN
Coordination compounds have been used from the earliest times as dyes
and pigments, for example madder dye which is red, was used by the ancient
Greeks and others. It is a complex of hydroxyanthraquinone. A more modern
example is the pigment copper phthalocyanine, which is blue.
2.
Analytical Chemistry
The coordination compounds used for various purpose, in the laboratary are as
follows.
a) Colour Tests : Since many complexes are highly coloured they can be used as
colourimetric reagents e.g. formation of red 2,2-bipyridyl and 1,10-phenanthroline
complexes as a test for Fe2+
b) Gravimetric Analysis : Here chelating ligands are often used to form
insoluble complexes e.g. Ni(DMG)2 and Al(oxine)3.
c) Complexometric Titrations and Masking Agents : An example of this
is the use of EDTA in the volumetric determination of a wide variety of metal ions
in solution, e.g. Zn2+, Pb2+,Ca2+,Co2+,Ni2+,Cu2+, etc. By careful adjustment of
160
the pH and using suitable indicators, mixtures of metals can be analysed, e.g. Bi3+
in the presence of Pb2+. Alternatively, EDTA may be used as a masking agent to
remove a metal ion which would interfere with the analysis of a second metal ion
present.
3.
Extraction of Metals
Bio-Inorganic Chemistry
Naturally occurring complexes include haemoglobin, chlorophyll, vitamin
B12 etc.
Therapeutic chelating agents are used as antidotes for heavy metal poisoning.
EDTA and other complexing agents have been used to speed the elimination
of harmful radioactive and other toxic elements from the body. (e.g. Pb2+). In
these cases a soluble metal chelate is formed.
5.
Chemotherapy
An example here is the use of cis-Pt(NH3)2Cl2 as an anti-tumour drug.
6.
Synthetic detergents
Haemoglobin
Chlorophyll
Ferredoxins Rubredoxins
Function
Transport and storage of oxygen
Photosynthesis
Electron Transfer
6.7.1 Haemoglobin
Haemoglobin in the red blood cells carries oxygen from the lungs to the
tissues. It delivers the oxygen molecule to myoglobin in the tissues. When the
oxygen has been released for cell respiration, haemoglobin loses its bright red
colour and becomes purple. It then combines with the waste carbon dioxide
produced by the cells and deposits in the lungs so that the gas can be exhaled.
Nature of haemoglobin and myoglobin
Both are having the same structure excepting the fact that myoglobin is a
monomer and haemoglobin is a tetramer. Both are iron-porphyrin complex.
These are biocoordination complexes formed between porphyrin and iron
in its +2 oxidation state (Fe2+). The iron-porphyrin complex is called the heme
group, which is a part of haemoglobin. Each haemoglobin molecule consists of
four subunits, each unit is being a folded chain.
The working part of haemoglobin is a hemegroup containing an Fe2+ cation
coordinated to four nitrogen atoms of porphyrin group and one nitrogen atom of
histidine group. The sixth octahedral site is available to bind oxygen molecule.
6.7.2 Chlorophyll
Chlorophyll is a magnesium - porphyrin complex. The magnesium is at the
centre of the modified porphyrin ring septeon (corrin). The oxidation state of
magnesium is +2 (Mg2+). The modified porphyrin acts as the ligand.
There are several kinds of chlorophyll that vary slightly in their molecular
structure.
In plants, chlorophyll a is the pigment directly responsible for the
transformation of light energy to chemical energy. Hence in plants, the green
pigment chlorophyll helps photosynthesis. The conversion of atmospheric
carbondioxide and atmospheric moisture into carbohydrate and molecular oxygen
in the presence of sunlight, by the plant is called as photosynthesis. Chlorophyll
acts as a light sensitiser in this important process.
xCO 2 + yH 2O chlorophyl
l Cx(H 2O)y + O 2
sunlight
162
3.
4.
5.
b) Chloro
d) triangular
b) -1
c) +2
d) -2
[Cu(NH3)4]Cl2
K3[Fe(CN)6]
b)
d)
K4[Fe(CN)6]
[NiCl4]2-
b)
d)
Square planar
Octahedral
9.
c) Octahedral
8.
b) square planar
7.
d) en
6.
c) Bromo
Tetrahedral
Triangular
c) NO2-
b) Cl163
d) I-
b) F- is a strong ligand
d) F- is a chelating ligand
b) Fe+2
c) Fe+3
d) CN-
b) 4
c) 5
d) 6
b) CN-
c) FeII
d) [Fe(CN)6]4-
15. A metal ion from the first transition series forms an octahedral complex with
magnetic moment of 4.9 BM and another octahedral complex which is
diamagnetic. The metal ion is
a) Fe2+
b) Co2+
c) Mn2+
d) Ni2+
c) BM
d) ergs
b) K Joules
b) Coordination isomerism
d) Ionisation
18. Valence bond theory does not explain the property of complex compound
a) geometry
b) magnetic
c) nature of ligand
d) colour
b) Na[B(NO3)4]
b) Na[B(NO3)4]
b) [Fe(CN)6]4-
b) K3[Fe(CN)6]
2.
166
7. NUCLEAR CHEMISTRY
Learning Objectives
( Review of basic nuclear chemistry.
( Know about the nuclear reactions and chemical reactions.
( Learn about nuclear energy and nature of nuclear fission and nuclear
fusion reactions.
( Learn about principle of nuclear reactors.
( Know about the nuclear reactions in sun.
( Learn about the application of radioactive isotopes including tracer technique
adopted in understanding reaction mechanisms.
Henry Becquerel (France) was awarded nobel prize for his discovery of
spontaneous radioactivity in 1903.
In the same year Pierre Curie (France) and Mary Curie (France) were
awarded for their research on radiation phenomenon. In 1911, Marie Curie
(France) was awarded nobel prize for the discovery of radium and polonium,
and the isolation of radium. In 1938, Enrico Fermi (Italy) was awarded
Nobel Prize for the discovery of nuclear reactions induced by slow neutrons.
167
Nuclear Chemistry
*
= decay constant
2.303
N0
N
log
N0
N
Half life period : The time required to disintegrate one half of any radioactive
substance is called half life period (t). The half life period (t) of a
radioactive substance is independent of initial concentration. It depends only
on the disintegration constant () of the radioactive element. t is used to
indicate the relative stability of radioactive substance. If t is the shorter,
faster is the rate of decay and hence the substance is more unstable and
viceversa.
0.693
t =
1
t
=
= 1.44 t
0.693
168
An - particle is equal to the bundle of two protons and two neutrons and
hence it is equal to the Helium nucleus (2He4).
169
Chemical reactions
Nuclear reactions
1.
2.
4.
5.
The following facts are taken into account while expressing a nuclear reaction:
i)
Reactions are written like a chemical equation. Reactants are written on the
left hand side and products on the right hand side with an arrow in between.
ii)
Mass number is written as super script on the symbol of the element. For
example 7N14 stands for an atom of nitrogen with mass number 14 and
atomic number 7.
iii)
neutron
proton
particle
deuteron
electron or -particle
positron
170
N14
He4
O17
projectile
H1
ejected particle
17
Cl37 + 1H2
17
Cl37 + 1H2
18
Ar38 + ?
Solution
18
Ar38
x1
x is neutron
Hence
17
Cl37 + 1H2
18
Ar38 + 0n1
Cl37 (D, n)
18
Ar38
mr
mp
In the case of energy absorbed then mp>mr, then Q value will be positive.
Q value of a nuclear reaction in the case of energy released = (mpmr)
931 MeV. In the case of energy released, mr>mp, and hence Q value will be
negative.
171
Spallation reaction
These are the reactions in which high speed projectiles may chip a heavy
nucleus into several fragments.
29
2.
Nuclear fission is the process in which a heavy nucleus breaks up into two
lighter nuclei of almost equal size with the release of an enormous amount of
energy. This type of nuclear fission reaction was first observed by German
Chemists Otto Hahn, F.Strassman and Meitner by bombarding 92U235 with slow
moving neutrons. The process is usually accompanied by emission of neutrons.
The nuclear fission has been produced in heavy nuclei such as 235U,238U, 232Th
by neutrons, protons, deuterons.
Mechanism of fission
In the fission process, the heavy nucleus absorbs a neutron and forms an
unstable compound nucleus. The compound nucleus then breaks up more or less
in the middle to give fission product.
Example
A typical example of the fission process in the fission of uranium by neutrons
is explained by the following equation.
92
U235 + 0n1
56
Further, the neutrons released (say three) from the fission of first uranium atoms
can hit three other uranium atoms. In this way a chain reaction is set up resulting
into the liberation of an enormous amount of energy. In the case of nuclear fission,
U236 formed breaks up in several ways.
92
140
92
235
+ 0n
1
92
93
B a + 36K r + 3 0n
144
+ 38 S r 90 + 2 0 n 1
5 4X e
144
90
1
+ 3 7R b + 2 0n
55C s
56
236
172
This fission process is self multiplying process and hence a tremendous amount
of energy is released in a very short interval of time. Therefore, explosion takes
place. Atom bomb is based on nuclear fission process.
Energy released in nuclear fission reaction
92
U235 + 0n1
42
Mo95
57
3)
Nuclear Fusion
When lighter nuclei moving at a high speed are fused together to form a
heavy nucleus, the process is called nuclear fusion.
In fusion reaction, the mass of heavier nucleus formed is less than the total
mass of two lighter nuclei. Thus, just like a fission reaction, the source of energy
in a fusion reaction is also the disappearance of mass, which gets converted into
energy.
Nuclear fusion reaction takes place at very high temperature of about 108K.
Therefore, this reaction is called thermonuclear reaction.
H2 + 1H3
Deuterium Tritium
1
He4 + 0n1 +
Helium
Energy
The Mass loss is equal to 0.018 amu and the corresponding energy released
is 1.79 109 KJmol-1.
Hydrogen Bomb
The highly destructive hydrogen bomb is also based on the fusion reactions
of hydrogen to form helium producing large amount of energy. Hydrogen bomb
consists of an arrangement for nuclear fission in the centre surrounded by a mixture
of deuterium (1H2) and lithium isotope (3Li6). Fission reaction provides the high
temperature necessary to start the fusion.
Fusion reactions take place in hydrogen bomb.
i)
ii)
Fission
Li6 + 0n1
3
H2 + 1H3
1
heat + neutrons
H3 + 2He4 + 4.78 MeV
1
He4 + 0n1 + 17.6 MeV
2
N 14 +
n1
C 14 + 1H1
The C14 atoms thus produced are rapidly oxidised to 14CO2 which in turn is
incorporated in plants as result of photosynthesis. Animals too consume C14 by
174
eating plants. On death, organisms cease to take in fresh carbonations. Carbon14 begins to decay.
6
C 14
N 14 +
-1
e0
5700 years a fossil (plant or animal) will lose half the amount of carbon-14
present in its living state. Therefore by knowing either the amount of C14 or the
number of -particles emitted per minute per gram of carbon at the initial and
final stages, the age of carbon material can be determined by the following equation.
t=
2.303 t
0.693
log
Uses
1)
Carbon dating has proved to be a great tool for correlating facts of historical
importance.
2)
It is very useful in understanding the evolution of life, and rise and fall of
civilizations.
4
0
fusion
2He + +1e + energy
175
O
*
+ HOH
R -C
R -C
+ R - OH
*
OH
Therefore it is the acid and not alcohol produced which is radioactive confirming
the above mechanism.
OR
Use
H3
Tritium
C 11
Carbon - 11
Brain scan
C 14
Carbon - 14
Radio immunology
I131
Iodine - 131
Hg197
Mercury - 197
Kidney scan
15
P 32
Phosphorous-32
26
Fe59
Iron - 59
Diagnosis of anemia
27
Co60
Cobalt - 60
Treatment of cancer
53
80
176
Na24
Sodium - 24
Au198
Gold - 198
Curing of cancers
11
79
Sr90
Practice Problems
1)
U235 + 0n1
42
U235 + 0n1
42
Solution
N0 = 1g
=
N = 0.125 g, t = 24 hours
2.303
N
log 0
t
N
2.303
1
log
24
0.125
= 0.0866 hour-1
=
t =
0.693 0.693
=
= 7.99 hours
0.0866
177
2.
Solution
t
=
= 100 sec
0.693
t
0.693
= 0.00693 sec 1
100
1
1
=
= 144.3 sec
0.00693
For 90% decay, N0 = 100; N = (100 - 90) = 10
3.
t =
2.303
2.303
0.00693
log
2.303
0.00693
log
N
N
100
10
Solution
t = 5.26 years
0.693
year1
5.26
= 4 years
N
Here to find the % of activity (i.e) to find N
0
2.303
N
log 0
=
t
N
178
log
t
2.303
N0
=
N
0.693
4
5.26 2.303
0.2288
Antilog (0.2288)
N0
N
=
N
N0
1.693
1
1.693
0.59 100
59%
% of activity =
=
4.
= 0 .59
Wooden artifact and freshly cut tree are having 7.6 and 15.2 counts
min-1g-1 of carbon (t = 5700 years) respectively. Calculate the age of the
artifact.
Age of the artifact
But
t =
0.693
0.693
t
0.693
Amount of old wood
2.303 5700
15.2
log
0.693
7.6
= 5700 years
5.
Half life period of a radio active element is 1500 years. Find the value of
disintegration constant interms of second.
179
=
=
0.693
0.693
=
t
1500 yrs
0.693
1500 365 24 60 60 sec
0.693
sec 1
4
4730 4 10
= 0.1465 10-10 sec-1
=
6.
The atomic masses of Li, He and proton are 7.01823 amu, 4.00387 amu
and 1.00715 amu respectively. Calculate the energy evolved in the reaction,
Li7 + 1H1 2 2He4 + E Given 1 amu = 931 MeV.
3
Solution
Mass of reactants = mass of Li + mass of H
= 7.01823 + 1.00715
= 8.02538 amu
180
Solution
92
Solution
0.693
= 0.693
t =
( Average life, =
t
0.693
140
days
0.693
= 202.02 days
=
181
1
)
2.303
N
log 0
t
N
2.303
100
log
90
12.5
= 0.02558 log 8
= 2.311 10-2 days-1
=
t =
0.693
0.693
=
= 29.99 days
2.311 10 2
11. Calculate Q value of the following nuclear reaction 13Al27 + 2He4 14Si30 +
H1+ Q. The exact mass of 13Al27 is 26.9815 amu, 14Si30 is 29.9738, 2He4
1
is 4.0026 amu and 1H1 is 1.0078 amu.
m =
=
Q =
=
2.
3.
b) 6, 4
c) 4, 3
182
d) 8, 6
4.
5.
6.
7.
8.
9.
Radioactivity is due to
a) Stable electronic configuration
c) Unstable nucleus
d) positron decay
b) Stable nucleus
d) Unstable electronic configuration
10. Which of the following is used as neutron absorber in the nuclear reactor?
a) Water b) Deuterium c) Some compound of uranium d) Cadmium
B. Answer in one or two sentences
11.
12.
13.
14.
15.
16.
17.
18.
19.
183
iii)
96
18
Ar40 +
ii)
iii)
88
Ra236
iv)
92
U238
19
K40 + 0n1
+ 2He4
Ba143 + _______+0n1
184
30.
92
31. The atomic mass of Th is 232 and its atomic number is 90. In terms of its
radioactivity six and four particles are emitted. What is the mass number
and atomic number of the product.
32. Calculate the average life of 79Au198 leaving t = 150 days.
33. Complete the following
N14 +2He4 8O17 +
i)
ii)
92
U235 +0n1
iii)
29
Cu53
28
56
Ba137 + 36Kr93 +
Ni58 +
13
Al27 + ?
11
ii)
34
Se83 + ?
34
iii)
Na24 + 2He4
Se84 + rays
35. The decay constant for 6C14 is 2.31 10-4 year-1 calculate the half life period.
Summary
*
Nature of nuclear fission and nuclear fusion reactions are briefly explained.
Reference
1.
2.
185
PHYSICAL CHEMISTRY
8. SOLID STATE - II
Learning Objectives
( To study the analysis of crystal structure using X-rays.
( To recognise the properties and types of ionic crystals.
( To know the elementary idea about the conducting and
superconducting properties of crystals.
( To learn the nature of Amorphous solids.
188
REVIEW
Solids are characterised by incompressibility, rigidity and mechanical strength.
Solids are usually classified as either crystalline or amorphous. Crystalline solids
have definite and ordered arrangement of the constituents extended over a long
distance and is called a long-range order. They possess a sharp melting point.
Amorphous solids like glass, rubber etc., although possessing many characteristics
of crystalline solids such as definite shape, rigidity and hardness, but are devoid
of a regular internal structure and melt gradually over a range of temperature. For
this reason they are not considered as true solids but rather highly supercooled
liquids.
Crystallography : A study of internal structure of crystals. 1913 - English
physicists, Father and Son, William and Lawrence Bragg developed X-ray
crystallography further by establishing laws that govern the orderly arrangement
of atoms in crystal interference and diffraction patterns. They also demonstrated
the wave nature of X-rays. In 1915 William Bragg and Lawrence Bragg were
awarded Nobel prize for physics for X-ray analysis of crystal structure.
UNIT CELL
Unit cell is the smallest fundamental repeating portion of a crystal lattice
from which the crystal is built by repetition in three dimension.
Characteristic parameters of a unit cell
z
Interfacial angles : , ,
Primitives (Intercepts) : a, b, c
a
x
189
fcc
A face atom is shared equally between two unit cells and therefore a face
N
f
atom contributes only 2 to the unit cell.
Nc Nf 8 6
+
= + = 1+ 3 = 4
8
2
8 2
Nf = Number of
atoms at the
faces
Nf
BCC
In a bcc lattice, the body centred atom belongs exclusively to the unit cell.
The total number of atoms per unit cell in bcc
=
Nb
Nc Nb 8 1
+
= + = 1+1 = 2
8
1
8 1
Nc Ne
+
8
4
8 12
+
= 1+3=4
8 4
Ne
Ne
191
n = 2d sin
The Braggs equation gives the essential condition for diffraction to occur.
3)
S lit
P ath o f
R e co rd e r
D iffra cte d
X -ra y s
Io n isatio n
ch am b e r
In c id e n t
X -ra y s
Tu rn ta b le
C ry sta l
S ca le to m e asu re
ro tatio n o f cry sta l
For sodium chloride, the maximum reflection or peaks for 100 plane occurred
at = 5.9, 11.85 and 18.15. The sines of these angles are 0.103, 0.205 and
0.312 which are in the ratio 1:2:3. These peaks represent the first,second and
third order reflections. The ratio confirms the correctness of Braggs equation.
8.2 TYPES OF CRYSTALS
Crystals are classified into the following four types depending upon the
nature of the units which occupy the lattice points.
1. Molecular Crystals
3. Metallic Crystals
2. Covalent Crystals
4. Ionic Crystals
1.
2.
3.
4.
5.
6.
7.
AB
: CsCl
: 8
AB
NaCl
6
AB
FeS
6
AB
ZnO
4
AB AB
ZnS BN
4
3
Let us discuss the structure of CsCl for AB type. It is body centered cubic
system. The chloride ions are at the corners of a cube where as Cs+ ion is at the
centre of the cube or vice versa. Each Cs+ ion is connected with eight Cl- ion and
Cl- is connected with eight Cs+ ions.
+
Cs
Cl
Nc 8
= =1
8 8
Nb 1
= =1
1 1
Thus number of CsCl units per unit cell is one.
- Ti
- O x y g en
N a m issin g
C l m issin g
Schottky defects appears generally in ionic crystals in which the positive and
negative ions do not differ much in size.
Frenkel defects
This defect arise when an ion occupies an interstitial position between the
lattice points. This defect occurs generally in ionic crystals in which the anion is
much larger in size than the cation. AgBr is an example for this type of defect.
One of the Ag+ ion occupies a position in the interstitial space rather than its own
appropriate site in the lattice is shown in Fig. 8.4.
+
Ag
Br
+
Ag
Br
Br Ag
+
Ag Br
Ag
Br
+
Ag Br
Br
+
Ag
Br
+
Ag
Ag
Br
+
Ag
Br
Br
+
Ag
Br
+
Ag
Ag
Br
+
Ag
Br
Br
+
Ag
Br
+
Ag
Ag
Br
+
Ag
Br
Typical metals are good conductors of electricity while elements like silicon
and germanium are non conductors at ordinary temperature. However, they exhibit
appreciable conductivity upon addition of impurities as Arsenic and Boron. The
resulting materials are called semiconductors. Semi conductors which exhibit
conductivity due to the flow of excess negative electrons are called n-type
semiconductors. The conductivity due to the positive holes are called p-type
semiconductors. Semiconductors find application in modern devices as recitifiers,
transitors and solar cells.
8.4.1 Super conductors
R esistiv ity
N o rm al
m etal
S u p er co n d u cto r
Tc
2)
3)
Determine the number of formula units of NaCl in one unit cell. NaCl is face
centred cubic.
Solution
1
199
1 1 = 1Na + ion
At the cube centre ___________________
Total 4 Cl and 4Na+ ions
Hence, the unit cell contains four NaCl units.
2)
n = 1,
d=?
= 278
3)
Solution
1
Number of A type atoms in the unit cell, 8 = 1
8
1
=3
2
In a fcc lattice of A and B type atoms are present. A atoms are present at
the corners while B type are at face centres. If in each unit cell, one of the A
type atom is missing from the corner, what is the simplest formula of the
compound?
1 7
Number of atoms of A type in the unit cell = 7 =
8 8
1
=3
2
2.
3.
4.
5.
Calculate the angle at which (a) first order reflection and (b) second order
reflection will occur in an X-ray spectrometer when X-ray of wavelength
1.54A are diffracted by the atoms of a crystal, given that the interplanar
distance is 4.04A.
[Ans : 1059 ; 2224]
SELF EVALUATION
The number of chloride ions that surrounds the central Na+ ion in NaCl
crystal is_______.
(a) 12
2.
(b) 8
(c) 6
3.
(c)2 = nd sin
(d) n = 2d sin
4.
(d) 4
(c) Primitive
(d) Crystallography
The smallest repeating unit in space lattice which when repeated over and
again results in the crystal of the given substance is called
(a) Space lattice
201
(d) Isomorphism
5.
6.
7.
10.
11.
12.
13.
14.
15.
(d) FeS
(b)
(d)
n-type semiconductors
Insulators
9.
(c) CsCl
8.
(b)
(d)
Avogadro number
Order of reflection
202
(b)
AgCl
(c)
CsCl
(d)
FeS
203
Summary
The study of crystals by X-rays are discussed.Types of ionic crystals AB
and AB2 type are explained with examples. An elementary idea about imperfections
in solids. The properties of ionic crystals and nature and properties of glasses
are discussed. Braggs equation and its significance are discussed.
References
1)
2)
3)
4)
Physical Chemistry, Peter Atkins Julio de Paula, 7th Edition 2003, Oxford
Press.
204
9. THERMODYNAMICS II
Learning Objectives
( To review first law of thermodynamics and to know its limitations.
( To learn the definition of second law of thermodynamics and the
mathematical statements.
( To study the differences of spontaneous and non spontaneous reactions
with examples. Also to learn the mathematical representation of entropy
S.
( To learn about Gibbs free energy change and to know the relation
G =H-TS.
( To study the significance of G
205
thus % efficiency =
output
x 100
input
The machine can be a heat engine also. Consider a heat engine which has
an initial temperature T1 and final temperature as T2, then if T1>T2 then when
some amount of heat is being converted into work, T2 is the lowered temperature.
The efficiency is given by,
T T
1
2
% efficiency = T x 100
1
T2
% efficiency = 1 T x 100
1
By II law, T2<T1 % efficiency less than 100.
9.3 ENTROPY AND ENTROPY CHANGE
The entropy function S introduced in the second law of thermodynamics
is explained as below.
Entropy function S represents the ratio of the heat involved (q) to the
q
temperature (T) of the process. That is S = . This relation is valid only for
T
reversible processes. If a system is changed from state 1 to state 2 at constant
temperature and if q rev is the heat involved in the process, then entropy change
of the process (S) is given by,
2
S2 S1 = S
= =
q rev
T
where the process is a reversible one. Entropy (S) and the change in entropy of
207
the process (S) are each state functions even though q and q path functions.
In a reversible process, entropy of universe remains a constant.
S universe = S system + S surroundings
= Constant
T
T
2
1
= T q p, rev
1
1
S = T q v, rev
1
The term natural process means that the process is spontaneous and does
not need to be induced. In order to find out whether a process is spontaneous
or not, the entropy changes of the system and the surroundings for the stipulated
process is considered. If this change is positive i.e. if the entropy of the universe
increases, the process will take place spontaneously and irreversibly.
If the entropy change of the universe is zero or negative (S<0) the system
will behave as non spontaneous.
When the external pressure is less than the internal pressure of a gaseous
system, the gas expands spontaneously. When volume increases in expansion,
the disorder in the movement of gaseous molecules increases. Thus, spontaneous
processes are associated with increase in disorder. When disorder in a process
is favoured it occurs spontaneously and we say, the entropy change is positive.
Entropy is a measure of microscopic disorder in the system and also represents
spontaneity.
208
universe
= S system + S surroundings = 0.
H vap
Tb
vap
= 21cal.deg
.mole 1
Low boiling liquids such as hydrogen and Helium which boil only a little
above 0K.
ii)
Polar substances like water, alcohol which form hydrogen bonded liquids
and exhibit very high boiling points as well as high Hvap.
iii)
Liquids such as acetic acid whose molecules are partially associated in the
vapor phase and possess very low entropy vaporization which is very much
less than 21 cals/ mol/deg.
Those liquids that obey Troutons rule are said to behave ideally.
Example 1
The normal boiling point CCl4, CHCl3 and H2S are 76.7oC, 61.5oC and
59.6oC respectively. Calculate the molar heat of vapourisation of each liquid,
assuming ideal behaviour.
Since the liquids behave ideally, Troutons rule is obeyed.
Svap =
H vap
Tb
= 21cal.deg
.mole
209
-1
-1
Hvap of CCl4
Hvap of CHCl3
Hvap of H S
Characteristics of entropy S
i)
ii)
q rev
T(K)
q rev
. Since H is the heat absorbed (or) evolved in the process at
T
H
constant T and pressure P.S is also calculated from H as S =
where T
T
is the temperature of the process involving H, amount of enthalpy change, at
constant pressure.
S =
Example 2
Calculate the entropy change involved in the conversion of 1 mole of ice at
0oC and 1 atm to liquid at 0oC and 1 atm. The enthalpy of fusion per mole of ice
is 6008 J mol-1.
H2O (s)
Ice
S
fusion
C
0
273 K
H2O (l)
Water liquid
H fusion
6008 J.mol 1
=
=
Tm(K)
(0 + 273) K
Example 3
Calculate the change of entropy for the process, water (liq) to water (vapor,
373K) involving Hvap = 40850 J mol-1 at 373K.
Hvab
40850 J/mol
= 109.517 J.K.1 mol1
S vap = Tb (K) =
373 K
1 mole Sn (, 13oC).
= 13+273 = 286 K.
transition
Strans
H trans
2090 J.mol 1
=
Ttrans (K)
286 K
b)
Example 6
Calculate the entropy changes in the system, and in the surroundings and
the total entropy change in the universe when during a process 75 J of heat flow
out of the system at 55oC to the surroundings at 20oC.
Tsystem
= 273+55 = 328 K.
S univ
q system
75J
=
= 0.2287Jk 1
Ssystem = T
328K
system
SSurroundings
q surroundin gs
Tsurroundin gs
+ 75J
= + 0.260 JK 1
293K
P = 4.1 atm
Temperatur e =
S =
V = 2 lit
= 100 K.
q 3710 J
=
= = 37.1 J K-1mol-1.
T 100 K
products
reactants
213
compound
= S
compound
elements
Example 8
Calculate the standard entropy of formation Sf of CO2(g). Given the
standard entropies of CO2(g), C(s), O2(g) as 213.6, 5.740 and 205.0 JK-1
respectively.
Sf
compound
= Scompound Selements
= SCO2(g) [SC + SO2(g)] JK-1
(s)
G = E + PV - TS.
i.e.
G = 0,
i.e.
G < 0,
Equilibrium
(reversible)
Non spontaneous
(nonfeasible)
G = 0
H = 0
S = 0
G > 0
H > 0
S < 0
at constant P and T
G < 0
H < 0
S > 0
G is defined as (H-TS) where H and S are the enthalpy and entropy of the
system respectively. T = temperature. Since H and S are state functions, G
is a state function.
ii)
iii)
iv) G and G values correspond to the system only. There are three cases of
G in predicting the nature of the process. When, G<0 (negative), the
process is spontaneous and feasible; G = 0. The process is in equilibrium
and G > 0 (positive), the process is nonspontaneous and not feasible.
v)
q
and TS = q = heat involved in the process.
T
G = q w + PV q = w + PV
(or) G = w PV = network.
The decrease in free energy G, accompanying a process taking place at
constant temperature and pressure is equal to the maximum obtainable work
from the system other than work of expansion.
This quantity is called as the net work of the system and it is equal to
(w PV).
Net work = G = w PV.
G represents all others forms of work obtainable from the system such
as electrical, chemical or surface work etc other than P-V work.
Standard free energy (G)
Like standard enthalpy of formation of substances, standard enthalpy change
of a reaction, standard free energy of formation of substances and standard free
energy change of reactions are considered. The standard free energy value (G)
of all substances either elements or compounds may be calculated from H and
S values at standard conditions of temperature (298 K) and pressure (1 atm)
and the substance being present in the standard state.
i.e
G = H TS
equal to the difference between the total sum of the standard free energies of
products and the total sum of the standard free energies of reactants, at standard
conditions.
Greaction = G product G reactants
Greaction can also be calculated from Hreaction and Sreaction values. Hreaction
and Sreaction can be calculated from Hf and S values of respective product
and reactant molecules at the constant temperature and pressure.
Example 10
For a chemical reaction the values of H and S at 300 K are 10 k cal
mol-1 and 20 cal. deg-1 mol-1 respectively. What is the value of G of the reaction?
Calculate the G of reaction at 400 K assuming H and S values are constant.
Predict the nature of the reaction.
G = H TS
at 300 K; G = 10,000 20 300
= 16,000 cals. mole-1
at 400 K; G = 10,000 20 400
= 18,000 cals. mole-1
At 300 K and 400 K, the values of G reaction are negative (<0). Therefore
the reaction is spontaneous (feasible) at both temperatures.
Example 11
C6H6(l) is -631 kJ. mol-1 at 25C.
H for the reaction 3C2H2(g)
Calculate G reaction and predict the direction in which the reaction is
spontaneous at 1 atm pressure. Given SC2H2 = 200.8 JK-1mol-1 and
SC6H6=172.8 JK-1 mol-1.
3C2H2(g)
C6H6(l)
S = S products S reactants
= SC
6H6(l)
3 SC H
= 172.8 3 200.8
2 2
= 429.8 JK-1
G = H TS; T = 298K
H
CO2(g)
= 394.4 + 137.2 0
= 257.2 kJ mol-1
Greaction = 257.2 = Hreaction 300 Sreaction
Hreaction = 257.2 300 (0.094)
Hreaction = 285.4 kJ. mol-1
Greaction has ve value. Therefore the reaction is spontaneous.
Also Hreaction has ve value. Therefore the reaction is exothermic.
SELF EVALUATION
A. Choose the correct answer
1.
2.
b) H
c) S
d) G
b) increase in enthalpy
d) decrease of free energy
219
3.
4.
b) q = 0
c) E = q
d) PV =0
5.
6.
Spontaneous
Reversible
b)
d)
Non-spontaneous
Equilibrium
7.
8.
H > 0, S > 0
H > 0, S < 0
b)
d)
H < 0, S > 0
H < 0, S < 0
9.
b) rusting of iron
d) vaporisation of camphor
G = H + TS
G = H TS
G = H TS
None of the above
a)
d)
For the reaction 2Cl(g) Cl2(g), the signs of H and S respectively are
a) +,
b) +, +
c) ,
220
d) , +
25. Predict whether the reaction CO(g) + H2O(g) CO2(g) + H2(g) is spontaneous
or not. The standard free energies of formation of CO(g), H2O(g) and CO2(g)
are 137.27, 228.6 and 394.38 kJ mole-1 respectively.
[Ans : Gr = 28.51 kJ]
26. Calculate the standard free energy change of the reaction : 4NH3(g) + 5O2
4NO(g) + 6H2O(l) and predict on the feasibility of the reaction. Standard
free energies of formation of NH3(g), NO(g) and H2O(l) are 16.65, 86.61,
237.20 kJ. mole-1 respectively.
[Ans : 1010.02 kJ mole-1]
27. The standard heat of formation of H2O(l) from its elements is 285.83 kJ.
mole-1 and the standard entropy change for the same reaction is 327 JK-1
at 25C. Will the reaction be spontaneous at 25C?
[Ans : Gr = ve; spontaneous]
28. The boiling point of benzene at 1 atm is 80.2C. Calculate the enthalpy of
vaporisation of benzene at its b. pt.
[Ans : 30.022 kJ.mol-1]
29. The standard entropy change Sr for
CH4(g) + 2O2(g)
CO2(g) + 2H2O(l)
is -242.98 JK-1 at 25C. Calculate the standard reaction enthalpy for the
above reaction if standard Gibbs energy of formation of CH4(g), CO2(g) and
H2O(l) are -50.72, -394.36 and - 237.13 kJ mol-1 respectively.
[Ans : Hr = 890.31 kJ.mol-1]
30. Standard enthalpy change for combustion of methane is 890 kJ mol-1 and
standard entropy change for the same combustive reaction is -242.98
J.K-1 at 25C. Calculate G of the reaction. [Ans : 817.6 kJ mole-1]
31. The standard entropy change for the reaction
9
O 3CO2(g) + 3H2O(l)
2 2(g)
is 339.23 JK-1 at 25C. Calculate the standard reaction enthalpy change
if the standard Gibbs energy of formation of C3H6(g), CO2(g) and H2O(l) are
62.78, 394.36 and 237.13 kJ.mol1 respectively.
[Ans : -2058.2 kJ mole-1]
C3H6(g) +
222
Summary
*
H vap
Tb
References
1)
2)
223
224
aA + bB
kr
cC + dD
Kc =
[C]c [D]d
[A]a [B]b
aA + bB + cC + ........
Kp =
then
p lL p mM p nN .....
paA p bB peC ......
where
pi
RT
since pi =
ni
RT
V
ni
= Ci = number of moles of i per litre. V = volume in litres.
V
p lL p mM p nN ..... 1
= a b e
p A p B p C ...... RT
226
Kp
(RT) ng
and Kp = Kc(RT)ng
2HI(g)
ng = 2-(1+1) = 2-2
Kp
Kp
= 0
= Kc (RT)O
= Kc
Case (ii)
When ng = +ve, the total number of moles of gaseous products are greater
than the total number of moles of gaseous reactants.
For example, 2H2O(g) + 2Cl2(g)
4HCl(g) + O2(g)
ng = (4+1) (2+2)
= 54=1
Kp
Kp
= Kc (RT)1
= Kc RT
and Kp > Kc
Case (iii)
When ng = ve, the total number of moles of gaseous products are lesser
than the total number of moles of gaseous reactants.
For example, consider the formation equilibrium of ammonia,
227
3H2(g) + N2(g)
ng = 2 (3+1)
= 2 4 = 2
K p = Kc (RT)-2
2NH3(g)
Kc
(RT) 2
< Kc
Kp =
and Kp
[SO3 ]2
dm 3 /mole
2
[SO 2 ] [O 2 ]
2SO2(g)+ O2(g)
[SO 2 ]2 [O 2 ] 1
=
mole/dm3
2
[SO3 ]
Kc
228
2HI(g)
[HI] 2
[H 2 ] [I 2 ]
(2x/V) 2
(a x) (b x)
V
V
4x 2
V2
= 2
V
(a x)(b x)
4x 2
=
= Kp
(a x)(b x)
x is also known as the extent of reaction.
Problem
Calculate the Kc, when a mixture containing 8.07 moles of H2 and 9.08 moles of
I2 are reacted at 448C until 13.38 moles of HI was formed at the equilibrium.
The reaction equilibrium is
H2(g) + I2(g)
Kc =
2HI(g)
(2x) 2
(a x)(b x)
229
a = 8.07 moles
b = 9.08 moles
x = 6.69 moles
Kc =
2x = 13.38 moles
(13.38)2
(8.07 6.69)(9.08 6.69)
= 54.29.
The equilibrium constant, Kc, value determines the direction and the extent
of the reaction that may proceed for maximum yield of the product for constant
conditions of temperature, pressure, initial concentrations of reactants or products
as applied on the reaction equilibrium.
In order to find the direction in which a reaction equilibrium may proceed
under different sets of initial concentrations of reactants and products which are
not equal to the respective equilibrium concentrations, a term known as reaction
quotient Q is used. Q is defined as the ratio of product of initial concentrations
of products to the product of initial concentrations of reactants under nonequilibrium conditions. For example, in the equilibrium.
lL + mM
aA + bB
Let [A], [B], [L] and [M] be the actual concentrations present before the
occurrence of equilibrium. These concentrations are considered as the nonequilibrium concentration conditions and the reaction quotient Q is given as
[L]l [M]m
Q=
[A]a [B]b
Let Kc be the equilibrium constant value of the equilibrium reaction in terms of
molar concentrations of reactants and products and the values of Kc and Q can
be compared.
When Q is greater than Kc (Q>Kc) the reaction will proceed so as to reduce
Q. That is, more of reactants will be formed from the products which means the
reverse reaction is favoured. When Q is lesser than Kc (Q<Kc) the reaction will
proceed so as to increase the concentration of products which is the forward
reaction. These aspects will hold good only when Q and Kc are under the same
conditions of temperature and pressure.
230
Problem
Initially, 0.1 moles each of H2 and I2 gases and 0.02 moles of HI gas
are mixed in a reaction vessel of constant volume at 300K. Predict the direction towards which the reaction proceeds [Kc = 3.5 10-2].
The formation equilibrium is
H2(g) + I2(g)
2HI(g)
Kc =
[HI] e2
= 3.5 10 2 at 300 K
[H 2 ]e [I 2 ]e
[HI]2
[H 2 ][I 2 ]
(2 10 2 ) 2
= 4 10 2
0.1 0.1
PCl3(g) + Cl2(g)
x/V x/V x 2
V
= 2
(a x)/V V (a x)
231
Kc =
x2
(a x)V
x =
Kc
x2P
______
(1x)RT
and K p =
p PCl 3 .p Cl 2
p PCl 5
atm
x 2P
atm
(1 x 2 )
x2
V
(or)
x V But V
x 2 = Kc V
1
P
1
P
232
Problem
Degree of dissociation of PCl5 at 1 atm and 25C is 0.2. Calculate the
pressure at which PCl5 is half dissociated at 25C.
For PCl5 dissociation equilibrium,
x 2P
Kp =
1 x2
Kp =
(0.2)2 (1.0)
0.04
0.04
=
=
= 0.042 atm
2
1 (0.2)
1 - 0.04 0.96
when x = 0.5, P = ?
P=
10.2
K p (1 x 2 )
x2
0.042(1 (0.5)2 )
0.042(1 0.25)
=
=
2
(0.5)
0.25
0.042(0.75 )
= 0.126 atm
0.25
Le Chateliers Principle
There are three major factors that alter the state of equilibrium. They are
concentration, temperature and pressure. The addition of a catalyst has no effect
on the state of equilibrium. Its presence merely hastens the approach of the
equilibrium.
Le Chateliers Principle
According to this principle, if a system at equilibrium is subjected to a
disturbance or stress, then the equilibrium shifts in the direction that tends to
nullify the effect of the disturbance or stress. Let us consider the effects of changes
in temperature, concentration and pressure, on the equilibrium reactions and the
predictions of Le Chateliers principle.
Effect of change of concentration
Consider the following equilibrium reaction
N2(g) + O2(g)
2NO(g)
233
At the equilibrium conditions the reaction mixture contains both the reactant and
product molecules, that is, N2, O2 and NO molecules. The concentrations of
reactant and product molecules are constant and remain the same as long as the
equilibrium conditions are maintained the same. If a change is imposed on the
system by purposely adding NO into the reaction mixture then the product
concentration is raised. Since the system possesses equilibrium concentrations
of reactants and products, the excess amount of NO react in the reverse direction
to produce back the reactants and this results in the increase in concentrations of
N2 and O2. Similarly if the concentration of reactants such as N2 and O2 are
purposely raised when the system is already in the state of equilibrium, the excess
concentrations of N2 and O2 favour forward reaction. Concentration of NO is
raised in the reaction mixture.
In general, in a chemical equilibrium increasing the concentrations of the
reactants results in shifting the equilibrium in favour of the products while increasing
the concentrations of the products results in shifting the equilibrium in favour of
the reactants.
Effect of change of temperature
A chemical equilibrium actually involves two opposing reactions. One
favouring the formation of products and the other favouring the formation of
reactants. If the forward reaction in a chemical equilibrium is endothermic
(accompanied by absorption of heat) then the reverse reaction is exothermic
(accompanied by evolution of heat).
Let us consider the example
N2O4(g)
2NO2(g) ; H = +59.0 kJ/mole
In this equilibrium, the reaction of the product formation (NO2) is endothermic
in nature and therefore, the reverse reaction of reactant formation (N2O4) should
be exothermic. If the above equilibrium reaction mixture is heated then its
temperature will be raised. According to Le Chateliers principle, the equilibrium
will shift in the direction which tends to undo the effect of heat. Therefore,the
equilibrium will shift towards the formation of NO2 and subsequently dissociation
of N2O4 increases. Therefore, generally, when the temperature is raised in a
chemical equilibrium, among the forward and reverse reactions, the more
endothermic reaction will be favoured. Similarly, if the temperature of the
234
equilibrium is decreased i.e., cooled, then the exothermic reaction among the
forward and reverse reaction of the equilibrium will be favoured.
Effect of change of pressure
If a system in equilibrium consists of reactants and products in gaseous
state, then the concentrations of all components can be altered by changing the
total pressure of the system. Consider the equilibrium in the gaseous state such as
N2O4(g)
2NO2(g)
Increase in the total pressure of the system in equilibrium will decrease the volume
proportionately. According to Le Chatliers principle, the change can be
counteracted by shifting the equilibrium towards decreasing the moles of products.
Hence, the reaction of combination of NO2 molecules to N2O4 formation will be
favoured.
In case of a gas phase equilibrium which is accompanied by decrease in
number of moles of products formed, the effect of pressure can be considered as
follows,
2NH3(g)
N2(g) + 3H2(g)
If the pressure is increased then the volume will decrease proportionately.
Consequently, the equilibrium will shift in the direction in which there is a decrease
in the total number of moles, ie., favours the formation reaction of NH3. Here
from four moles of reactants two moles of NH3 are formed. Thus at higher
pressures, the yield of ammonia will be more.
Habers Process
Ammonia is mainly used as a source of nitrogen fertiliser, in nitric acid
production and in nitrogen containing pharmaceuticals. Ammonia is commercially
produced in industries from the gaseous elements nitrogen and hydrogen in air by
means of Habers process. Ammonia formation reaction is an equilibrium reaction.
Fe
N2(g) + 3H2(g)
2NH3(g)
such a reaction and shifts the equilibrium towards the product formation direction.
Therefore, nearly 300-500 atm pressure is applied on 3:1 mole ratio of H2:N2
gas mixture in the reaction chamber for maximum yield of ammonia. The ammonia
formation reaction is exothermic. By Le Chatliers principle, increase in temperature
favours decomposition reaction of ammonia. However, at low temperature the
time to reach the equilibrium becomes very long. Hence an optimum temperature
close to 500C-550C is maintained. Iron catalyst is chosen to speed up the
attainment of the equilibrium concentration of ammonia. In order to maintain the
equilibrium conditions, steam is passed to remove away the ammonia as and
when it is formed so that the equilibrium remains shifted towards the product
side. The maximum yield of ammonia is nearly 37%.
Contact Process
This process involves the equilibrium reaction of oxidation of SO2 gas by
gaseous oxygen in air to manufacture large quantities of SO3 gas.
v2o5
2SO2(g) + O2(g)
2SO3(g)
The formation reaction of SO3 involves a decrease in the overall moles of the
reactants. By Le Chatliers principle, when large pressure is applied, forward
reaction is favoured. 700 atm - 1200 atm pressure is maintained on the 2:1 mole
ratio mixture of pure SO2 and O2 gases in the reaction chamber. SO3 production
is an exothermic reaction. Hence, increase in temperature favours SO 3
dissociation. However, lowering of temperature prolongs the time of attainment
of equilibrium. Therefore, an optimum temperature at nearly 400C to 450C is
maintained to favour the equilibrium.
The most widely used catalyst for SO3 production is porous vanadium
pentoxide (V2O5). Presence of moisture deactivates the catalyst. Only dry and
pure SO2 and O2 gases are used over the catalyst. Since oxidation of SO2 is a
slow process, presence of V2O5 speeds up the equilibrium process and high
yield of SO3 is achieved in a short period. SO3 is the anhydride of H2SO4.
Therefore, SO3 from contact process along with steam is used in oleum and
H2SO4 manufacturing processes in contact process, the yield of SO3 is nearly
97%.
236
SELF EVALUATION
A. Choose the correct answer
1.
2.
d) both
3.
c) none
d) K1 = 1/K22
c) K2 = (K1)2
b) K1 = 1/K2
B is K1
d) Zero
4.
5.
d) (mol dm-3)-9
6.
Two moles of ammonia gas are introduced into a previously evacuated 1.0
dm3 vessel in which it partially dissociates at high temperature. At equilibrium
1.0 mole of ammonia remains. The equilibrium constant Kc for the dissociation
is
a) 27/16 (mole dm-3)2
b) 27/8 (mole dm-3)2
c) 27/4 (mole dm-3)2
c) None of these
7.
10.
11.
12.
13.
14.
ii)
CO(g) + H2O(g)
iii)
N2O4(g)
CO2(g) + H2(g)
2 NO2(g)
lL + mM
[L]l [M]m k f
=
[A]a [B]b k r
References
1.
2.
240
rate =
k[A]p [B]q
p =
a or less than a
q =
b or less than b
... (11.1)
where k = rate constant of the reaction, p and q are the exponents or also
known as the orders with respect to reactants A and B respectively.
Therefore the term order can be defined as the sum of the powers of the
exponential powers to which each concentration term is raised in the
experimentally determined rate law of a chemical reaction.
In the rate expression (11.1),
rate = k[A]p, [B]q, p and q are called the orders of the reaction with
respect to reactants A and B respectively. The total order of the reaction,
n = p + q. Order with respect to A only p and order with respect to B only
is q.
It is found that the overall rate of a reaction, depends on the exponential
powers to which each concentration term is raised in the rate law. For
example, for a reaction with a rate law as rate = k[A]2, when the concentration
of A is doubled, the rate is increased by four times the initial rate. Thus,
chemical reactions and the over all rates are classified and studied according
to the magnitude of the order of their reactions.
Example
From the rate equations for the reactions given below determine the
order with respect to the overall reaction
(i)
2HCrO4 + 6I + 14H+
H2O2 + 2I + 2H+
Order = 1 + 2 + 2 = 5
I2 + 2H2O
Order = 1 + 1 = 2
r = k [H2O2] [I]
k1
Rate of reaction =
products
-d[A] = k
1.0
_____
1[A]
dt
... (11.2.)
dx
_____
(a x)
= k1
dt
... (11.3)
c = integration constant
at time, t = 0, x = 0.
in equation 11.3,
ln (a 0) = k1 0 + C
or C = ln a.
Substituting C value in equation 11.3
ln (a x) = k1t ln a
Rearranging,
(or)
k1 =
a
1
ln a x
t
k1 =
2. 303
a
log
t
ax
... (11.4)
Unit of k1 is sec1.
This equation is known as the first order rate constant equation.
This equation can be used for determining the rate constant of a first
order reaction based on the experimental data of (a) and (a x) at different
periods of time t. Sometimes, the following expression is also used.
2. 303
a x1
k1 = t t log a x
2
1
2
t1 and t2 periods of time.
t1/u =
and
t1/u
2. 303
a
log
a
= k1
a
u
2. 303
u
log
k1
( u 1)
90Th
234
2He
SO2(g) + Cl2(g)
H+
C6H12O6 +
Glucose
C6H12O6
Fructose
2NO2 + O2
There are many other reactions that proceed by first order kinetics. We
shall study some of the reactions that are experimentally followed by first
order kinetic expressions including the parameters that change with
concentration of the reactants or products which change with time of progress
of the reaction.
Let us consider some of the first order reactions in detail :
1. Decomposition of nitrogen pentoxide in CCl4
k1
N2O5
2NO2
+ O2
2. 303
V
log
sec 1
t
(V Vt )
10
15
20
Vol. of O2 (cc)
6.3
8.95
11.4
34.75
V = 34.75 cc
2. 303
V
log
sec 1
t
(V Vt )
1 min = 60 secs
6
t(min)
2. 303
V
k1 = t 60 log V V sec1
o
t
(V - Vt)
10
28.45
2. 303
34. 75
log
= 2.079 104 sec1
10 60
28. 45
15
25.8
2. 303
34. 75
4
1
15 60 log 25.8 = 1.530 10 sec
20
23.35
2. 303
34. 75
log
= 1.267 104 sec1
20 60
23. 35
Mean value = 1.6253 10-4 sec1
Pt
H2O + O2
Vo
2. 303
log V sec1.
t
t
7
10
20
30
40
vol of KMnO4
(CC)
25
20
15.6
12.7
9.4
time(min)
2. 303
Vo
k1 = t 60 log V sec1
t
Vt
10
20
2. 303
25
log
= 2.68 104 sec1
10 60
15. 6
20
15.6
2. 303
25
4
1
20 60 log 15. 6 = 1.72 10 sec
30
12.7
2. 303
25
4
1
log
30 60
12. 7 = 1.42 10 sec
40
9.4
2. 303
25
4
1
log
40 60
9. 4 = 1.43 10 sec
k1 =
2. 303
a
log
t
ax
a
t =
2. 303
a
log
k1
aa / 2
t =
2. 303log 2. 0
k1
t =
0. 693
k1 secs.
Thus half life period of a first order reaction is independent of the initial
concentration of the reactant and also, inversely proportional to the rate
constant of the reaction.
Example : Compound A reacts by first order kinetics. At 25C, the rate
constant of the reaction is 0.45 sec1. What is the half life of A at 25C.
What is the time required to have 12.5% unreacted A for first order reaction,
t =
0. 693 0. 693
k1 = 0. 45
= 1.54 secs
No. of t
50%
25%
12.5%
Example : Show that for a first order reaction time required for 99%
completion is twice the time required for 90% completion of the reaction.
t99% =
2. 303
100
2. 303
log
=
log 100
k1
100 99
k1
t90% =
2. 303
100
2. 303
log
=
log 10
k1
100 90
k1
t99%
log 100
2. 0
=
=
= 2.0
t90%
log 10
1. 0
FG IJ
H K
t1
a2
=
t2
a1
n 1
a1
a2
263
=
212
FG 360 IJ
H 290 K
n 1
1.24 = (1.24)n1
n1= 1
n
= 1+1=2
2. 303
a
2. 303
a
log
log
=
t
ax
40.5 min
0. 75a
t99.9% =
2. 303
a
log
k
ax
2. 303
100
log
100 99. 9
k
2. 303
100
log10
k
0.1
2. 303
log10 1000
k
t(50%) =
... (1)
2. 303
100
log10
100 50
k
2. 303
100
log10
k
50
2. 303
log10 2
k
... (2)
11
(1)
(2)
t(99.9%)
t(50%)
2. 303
log10 1000
k
= 2. 303
log10 2
k
3. 000
= 10
0. 3010
0. 693
k
0. 693
= 450 seconds.
1.54 103 sec 1
k2
Rate = k2 [A] [B] where k2 is the rate constant of the second order
reaction. If concentration of A is very large compared to concentration of
B, then during the reaction amount of A consumed will be equal to the
amount of B reacting with A. Since B concentration is smaller than that of
12
H+
CH3COOH + CH3OH
Methyl acetate
... (11.7)
1000
18
= 55.55 moles
(a x )
(V Vo )
= (V V )
t
The first order rate expression for the hydrolysis of ester can be
written as
(V Vo )
2. 303
log10 (V V )
t
t
k =
20
40
60
v (mL)
20.2
25.6
29.5
32.8
50.4
(V Vo )
2. 303
log (V V )
t
t
50. 4 20. 2
2. 303
log 50. 4 25. 6
20
= 0.1151 log
30. 2
24.8
k =
50. 4 20. 2
2. 303
log 50. 4 29.5
40
= 0.0576 log
30. 2
= 0.0576 0.1596
20. 9
50. 4 20. 2
2. 303
30. 2
log 50. 4 32.8 = 0.03838 log
60
17. 6
... (1)
... (2)
Ea
= 2. 303 R
k2
log k
1
Ea
= 2. 303 R
FG T T IJ
H TT K
FG T T IJ
H TT K
1
1 2
1 2
log k
slope = Ea/2.303 R.
1/T (K1)
Reactant molecules come into contact through collisions for
transformation into product molecules. Since, not all collisions are successful
in producing the product molecules, all colliding molecules must possess
certain minimum energy called as the threshold energy which is needed to
make the collisions effective and successful. The additional energy required
17
P.E. of products
Ea
P.E.
o
f re
acta
nts
Energy
Threshold energy
Ea = activation energy
Reaction Co-ordinate
k 105 sec1
25
3.46
35
13.50
Ea
FG T T IJ
H TT K
2
1 2
18
Ea
= 2. 303 1. 987
Ea =
FG 308 298 IJ
H 308 298 K
= 2.4830 cals.
Ea
log k
2
k1
k
2
Ea
2. 303 R
LM 1 1 OP
NT T Q
2
100000 J / mol
2. 303 8. 314 JK 1mol 1
= 0.5745
k1
k
2
= antilog (0.5745)
= 0.2664
19
LM 1 1 OP
N 308 298 Q
k2 =
1
k = 3.75 times k1.
0. 2664 1
k2, the rate constant at 35C will be 3.75 times the rate constant at
25C.
Example : Decomposition of ethyl bromide and propyl bromide follow
first order kinetics, and have the same frequency factor A. The rate constant
for decomposition of ethylbromide at 390C is same as that for propylbromide
at 320C. If the Ea of ethyl bromide reaction is 230 KJ/mole, what is the Ea
of propylbromide reaction ?
For ethyl bromide decomposition at 390oC
230000
... (1)
... (2)
Ea
Ea =
230000 593
663
Ea = 205.7 kJ/mole.
11.5 SIMPLE AND COMPLEX REACTIONS
A simple reaction takes place in a single step. Simple reactions are also
known as elementary reactions. One step reactions are elementary reactions.
In some reactions many side reactions occur along with the main reaction
involving product formation.
20
Reactions which do not take place in a single step but take place in a
sequence of a number of elementary steps are called as complex reactions.
Simple reactions
Complex reactions
1.
2.
3.
No side reactions
4.
5.
k1
k2
21
k1
R'OOC(CH2)nCOOH
k2
Bromination of bromobenzene :
Br
Br
+ HBr
Br
o-dibromobenzene
Br
+ HBr
Br
p-dibromobenzene
22
(ii)
Dehydration of 2-methyl-2-butanol
CH3
|
H3CCCH2CH3
|
OH
CH3
|
CH3C=CHCH3
2-methyl 2-butene
2-methyl-2-butanol
CH3
|
CH2 = CCH2CH3
2-methyl1-butene
kf
C + D,
kr
Examples of opposing reactions
(i)
(ii)
kf
kr
CO2(g) + NO(g)
H2C CH2
(iii)
kf
kr
CH3 CH = CH2
H2(g) + I2(g)
23
SELF EVALUATION
(A) Choose the correct answer :
1. Hydrolysis of an ester by dilute HCl is an example for
(a) second order reaction
(b) zero order reaction
(c) pseudo first order reaction (d) first order reaction
2. The unit of zero order rate constant is
(b) mol litre1 sec1
(a) litre mol1 sec1
1
(c) sec
(d) litre2 sec1
3. The excess energy which a molecule must posses to become active is
known as
(a) kinetic energy
(b) threshold energy
(c) potential energy
(d) activation energy
4. Arrhenius equation is
(a) k = Ae1/RT (b) k = AeRT/Ea
6. The sum of the powers of the concentration terms that occur in the rate
equation is called
(a) molecularity (b) order
(c) rate
7. Reactions in which the reacting molecules react in more than one way
yielding different set of products are called
(a) consecutive reactions
(b) parallel reactions
(c) opposing reactions
(d) chain reactions
8. The half life period of a first order reaction is 10 minutes. Then its rate
constant is
(a) 6.93 102 min1
(b) 0.693 102 min1
2
1
(c) 6.932 10 min
(d) 69.3 101 min1
9. For a reaction : aA
bB, the rate of reaction is doubled when the
concentration of A is increased by four times. The rate of reaction is
equal to
24
(a) k [A]a
10. 2N2O5
(b) k [A]
4NO2 + O2,
d [N O2 ]
d [O2 ]
= k2 [N2O5] and
= k3 [N2O5], the relation between k1, k2
dt
dt
and k3 is
(a) 2k1 = 4k2 = k3
(c) 2k1 = k2 = 4k3
(b) k1 = k2 = k3
(d) 2k1 = k2 = k3
11. For a reaction, Ea = 0 and k = 4.2 105 sec1 at 300K, the value of k at
310K will be
(a) 4.2 105 sec1
(b) 8.4 105 sec1
(c) 8.4 105 sec1
(d) unpredictable
(B) Answer in one or two sentences :
1. Define order of a reaction.
2. Derive the relationship between half-life period and rate constant for a
first order reaction.
3. What is activation energy ?
4. What is meant by zero order reaction ? What is the rate constant of such
a reaction ?
5. Write the Arrhenius equation and explain the terms.
6. Define half life period.
7. Give examples for first order reaction.
8. What are simple and complex reactions ?
9. Give examples for opposing reactions.
(C) Answer not exceeding sixty words :
1. Explain the experimental determination of rate constant of acid hydrolysis
of methyl acetate.
2. Write an account of the Arrhenius equation for rates of chemical reactions.
25
t (a)(1n).
REFERENCES :
1.
2.
3.
27
1. Physical adsorption
This adsorption is due to the operation of forces between solid surface
and the adsorbate molecules that are similar to vander waals forces between
molecules. These forces are generally undirected and relatively non specific.
Physical adsorption can also be defined as that type of adsorption where
physical forces hold the gas molecules to the solids.
2. Chemical adsorption
Chemical adsorption is defined as a type of adsorption in which chemical
bonds serve the function of holding gas molecules to the surface. It occurs
due to the stronger binding forces, comparable with those leading to formation
of chemical compounds. It is generally an irreversible process.
The main differences can be summarised as follows:Physical adsorption
Chemical adsorption
1. It is due to intermolecular
Vander waals force.
4. Reversible.
4. Irreversible.
i. Temperature
ii. Pressure
iii. Nature of the gas and
iv. Nature of the adsorbent.
Effect of temperature and pressure
Adsorption is invariably accompanied by evolution of heat. Therefore,
in accordance with Le chateliers principle, the magnitude of adsorption
increases with decrease in temperature. Further, since adsorption of a gas
leads to decrease of pressure, the magnitude of adsorption increases with
increase in pressure. Thus, decrease of temperature and increase of pressure
both tend to cause increase in the magnitude of adsorption of a gas on a
solid.
Nature of the gas
It is observed that the more readily soluble and easily liquefiable gases
such as ammonia, chlorine and sulphur dioxide are adsorbed more than the
hydrogen, nitrogen and oxygen. The reason is that Vander waals or
intermolecular forces which are involved in adsorption are more predominant
in the former than in the latter.
Nature of the adsorbent
Adsorption is a surface phenomenon. Therefore, the greater the surface
area per unit mass of the adsorbent, the greater is its capacity for adsorption
under the given conditions of temperature and pressure.
12.2 CATALYSIS
A catalyst is a substance which alters the speed of a chemical reaction
without itself undergoing any chemical change and the phenomenon is known
as catalysis.
Example,
2KClO3
MnO2
2KCl + 3O2
2SO3
CH3COOH + CH3OH
31
2. Heterogeneous Catalysis
The catalytic process in which the reactants and the catalyst are in
different phases is known as heterogeneous catalysis. Some of the examples
of heterogeneous catalysis are given below.
i. Oxidation of SO2 to SO3 in the presence of Pt metal or V2O5 as catalyst
in the contact process for the manufacture of sulphuric acid.
Pt(s)
2SO2(g) + O2(g)
2SO3
The reactants are in gaseous phase while the catalyst is in solid phase.
ii. Combination between nitrogen and hydrogen to form ammonia in the
presence of finely divided iron in Habers process.
Fe(s)
N2(g) + 3H2(g)
2NH3
The reactants are in gaseous phase while the catalyst is in solid phase.
Types of catalysts
The catalysts have been divided into different types according to their
behaviour and pattern of action.
1. Positive catalyst
A catalyst which enhances the speed of the reaction is called positive
catalyst and the phenomenon is known as positive catalysis. Various examples
are given below :
i. Decomposition of H2O2 in presence of colloidal platinum
Pt
2H2O2
2H2O
O2
MnO2
2KCl
32
3O2
2. Negative Catalyst
There are certain substances which, when added to the reaction mixture,
retard the reaction rate instead of increasing it. These are called negative
catalysts or inhibitors and the phenomenon is known as negative catalysis.
The examples are given below.
i. The oxidation of sodium sulphite by air is retarded by alcohol.
Alcohol
2 Na2SO3
+ O2
2 Na2SO4
2 H2O2
2 H2O +
O2
3. Auto catalyst
In certain reactions, it is observed that one of the products formed during
the reaction acts as a catalyst for that reaction. Such type of catalyst is called
auto catalyst and the phenomenon is known as auto catalysis.
In the oxidation of oxalic acid by potassium permanganate, one of the
products MnSO4 acts as a auto-catalyst because it increases the speed of the
reaction.
5
COOH
|
+ 2 KMnO4 + 3 H2SO4
COOH
4. Induced Catalyst
When one reactant influences the rate of other reaction, which does not
occur under ordinary conditions, the phenomenon is known as induced
catalysis.
Sodium arsenite solution is not oxidised by air. If, however, air is passed
through a mixture of the solution of sodium arsenite and sodium sulphite,
both of them undergo simultaneous oxidation. Thus sulphite has induced
the arsenite and hence is called induced catalyst.
33
Promoters
The activity of a catalyst can be increased by addition of a small quantity
of a second material. A substance which, though itself not a catalyst, promotes
the activity of a catalyst is called a promoter. Some examples of the promoters
are given below.
i. In the Habers process for the synthesis of ammonia, traces of
molybdenum increase the activity of finely divided iron which acts as a
catalyst.
Fe
N2
+ 3 H2
2 NH3
+ Mo
Catalytic Poisons
A substance which destroys the activity of the catalyst is called a poison
and the process is called catalytic poisoning. Some of the examples are
(i) The platinum catalyst used in the oxidation of SO2 in contact process
is poisoned by arsenious oxide.
Pt
SO2
O2
2 SO3
Poisoned
by As2O3
(ii) The iron catalyst used in the synthesis of ammonia in Haber process
is poisoned by H2S
Fe
N2
+ 3 H2
2 NH3
Poisoned
by H2S
Active Centres
The catalytic surface has unbalanced chemical bonds on it. The reactant
gaseous molecules are adsorbed on the surface by these free bonds. This
34
accelerates the rate of the reaction. The distribution of free bonds on the
catalytic surface is not uniform. These are crowded at the peaks, cracks and
corners of the catalyst. The catalytic activity due to adsorption of reacting
molecules is maximum at these spots. These are, therefore, referred to as
the active centres. If a catalyst has more active centres, then its catalytic
activity is increased.
12.3 THEORIES OF CATALYSIS
There are two main theories to explain catalysis.
1. Intermediate compound formation theory
2. Adsorption theory
In general, the intermediate compound formation theory applies to
homogeneous catalytic reactions and the adsorption theory applies to
heterogeneous catalytic reactions.
The Intermediate Compound Formation Theory
According to this theory, the catalyst first forms an intermediate
compound with one of the reactants. The compound is formed with less
energy consumption than needed for the actual reaction. The intermediate
compound being unstable combines with other reactant to form the desired
product and the catalyst is regenerated.
For example, a reaction of the type
A + B
AB
A + C
Catalyst
AC
Intermediate
compound
+ B
AB + C
Product
Catalyst
+ O2
2NO2
Catalyst
NO2
Intermediate
compound
+ SO2
SO3
Product
+ NO
Catalyst
Adsorption Theory
This theory explains the mechanism of heterogeneous catalysis. Here,
the catalyst functions by adsorption of the reacting molecules on its surface.
A(g) + B(g)
C(g) + D(g)
Catalyst
Nitric oxide.
12.4 COLLOIDS
Thomas Graham, in 1861, during his work on diffusion, found that while
certain substances, such as sugars, salts, acids and bases diffused readily
through a parchment membrane, others, such as gelatin, albumen and glue,
diffused at a very slow rate. The substances belonging to the former category
37
which generally exist in crystalline state, were called crystalloids while the
substances belonging to the second category were given the name colloids.
These observations led to the development of a new branch known as colloidal
science.
In a true solution as sugar or salt in water, the solute particles are
dispersed in the solvent as single molecules or ions. Thus the diameter of the
dispersed particles ranges from 1A to 10A. On the other hand, in a
suspension as sand stirred into water, the dispersed particles are aggregates
of millions of molecules. The diameter of these particles is of the order of
2000A or more. The colloidal solutions are intermediate between true
solutions and suspensions. When the diameter of the particles of a substance
dispersed in a solvent ranges from about 10A to 2000A, the system is
termed a colloidal solution.
Types of Colloids
A colloidal system is made up of two phases. The substance distributed
as the colloidal particles is called the dispersed phase. The second continuous
phase in which the colloidal particles are dispersed is called the dispersion
medium. Depending upon the physical state of dispersed phase and dispersion
medium, the following types of colloidal solutions are possible.
Dispersed
phase
Dispersion
medium
Name
Examples
Solid
Solid
Solid-sol
Solid
Liquid
Sol
paint, ink
Solid
Gas
Aerosol
Smoke, haze
Liquid
Solid
Gel
Curd, cheese
Liquid
Liquid
Emulsion
Milk, Cream
Liquid
Gas
Liquid Aerosol
Cloud, mist
Gas
Solid
Solid form
Gas
Liquid
Foam
Froths of air
38
Condensation methods
1.
Mechanical dispersion
1. Exchange of solvents
2.
Electro-dispersion
3.
4.
Ultrasonic dispersion
Peptization
3. Chemical methods
i.
Double decomposition
ii.
Oxidation
iii. Reduction
iv. Hydrolysis
39
Dispersion Methods
1. Mechanical dispersion using colloidal mill
The solid along with the
liquid is fed into a colloidal
mill. The colloidal mill consists
of two steel plates nearly
touching each other and
rotating in opposite directions
with high speed. The solid
particles are ground down to
colloidal size and then
dispersed in the liquid.
Colloidal graphite and printing
inks are made by this method.
Fig. 12.2 Colloid mill
3. Ultra-sonic dispersion :
The sound waves of high frequency are usually called ultra-sonic waves.
Ultrasonic waves are passed through the solution containing larger particles.
They break down to form colloidal solution.
4. Peptisation :
The dispersion of a precipitated material into colloidal solution by the
action of an electrolyte in solution is termed as peptisation. The electrolyte
used is called a peptizing agent.
A few examples are
i. Silver chloride can be converted into a sol by adding hydrochloric
acid
ii. Ferric hydroxide yields a sol by adding ferric chloride
II. Condensation methods
1. By exchange of solvent
If a solution of sulphur or phosphorus in alcohol is poured into water, a
colloidal solution of sulphur or phosphorus is obtained due to low solubility
in water.
2. By change of physical state
Colloidal solutions of certain elements such as mercury and sulphur are
obtained by passing their vapour through cold water containing a stabiliser.
3. Chemical Methods
The chemical methods involve chemical reaction in a medium in which
the dispersed phase is sparingly soluble. Some of the methods are
(i) Double decomposition: An Arsenic sulphide sol is prepared by
passing a slow stream of hydrogen sulphide gas through a cold solution of
arsenious oxide. This is continued till the yellow colour of the sol attains
maximum intensity.
As2O3 +
3 H2S
As2S3 + 3 H2O
Yellow
41
2H2O + 3 S
(iii) Reduction: Silver sols and gold sols can be obtained by treating
dilute solution of silver nitrate or gold chloride with organic reducing agents
like tannic acid or formaldehyde.
AgNO3 + tannic acid
Ag Sol
Au Sol
Fe(OH)3 + 3HCl
red sol
PURIFICATION OF SOLS
In the methods of preparation stated above, the resulting sol frequently
contains besides colloidal particles appreciable amounts of electrolytes. To
obtain the pure sol, these electrolytes have to be removed. This purification
of sols can be accomplished by three methods:
(a) Dialysis
(b) Electrodialysis and
(c) Ultrafiltration
Dialysis
Animal membranes (bladder) or
those made of parchment paper and
cellophane sheet, have very fine
pores. These pores permit ions (or
small molecules) to pass through but
not the large colloidal particles.
Ultrafiltration
Sols pass through an ordinary filter paper. Its pores are too large to
retain the colloidal particles. However, if the filter paper is impregnated
with collodion or a regenerated cellulose such as cellophane or visking, the
pore size is much reduced. Such a modified filter paper is called an ultrafilter.
43
The separation of the sol particles from the liquid medium and electrolytes
by filtration through an ultrafilter is called ultrafiltration.
Ultrafiltration is a slow process.
Gas pressure (or suction) has to be
applied to speed it up. The colloidal
particles are left on the ultrafilter in
the form of slime. The slime may be
stirred into fresh medium to get back
the pure sol. By using graded
ultrafilters, the technique of
ultrafiltration can be employed to
separate sol particles of different
sizes.
Fig. 12.6 Ultra filtration
45
(ii) Fog, mist and rain : When a large mass of air, containing dust
particles, is cooled below its dewpoint, the moisture from the air condenses
on the surfaces of these particles forming fine droplets. These droplets being
colloidal in nature continue to float in the air in the form of mist or fog.
Clouds are aerosols having small droplets of water suspended in air. On
account of condensation in the upper atmosphere, the colloidal droplets of
water grow bigger and bigger in size, till they come down in the form of
rain. Sometimes, the rainfall occurs when two oppositively charged clouds
meet.
It is possible to cause artificial rain by throwing electrified sand or
spraying a sol carrying charge opposite to the one on clouds from an
aeroplane.
(iii) Food articles : Milk, butter, halwa, ice creams, fruit juices, etc.,
are all colloids in one form or the other.
(iv) Blood : Blood is a colloidal solution of an albuminoid substance.
The styptic action of alum and ferric chloride solution is due to coagulation
of blood forming a clot which stops further bleeding.
(v)Soils : Fertile soils are colloidal in nature in which humus acts as a
protective colloid. On account of colloidal nature, soils adsorb moisture and
nourishing materials.
(iv) Formation of delta : River water is colloidal solution of clay. Sea
water contains a number of electrolytes. When river water meets the sea
water, the electrolytes present in sea water coagulate the colloidal solution
of clay which get deposited with the formation of delta.
2. Technical Applications
(i) Electrical precipitation of smoke : Smoke is a colloidal solution
of solid particles such as carbon, arsenic compounds, dust, etc., in air. The
smoke, before it comes out from the chimney, is led through a chamber
containing plates having a charge opposite to that carried by smoke particles.
The particles on coming in contact with these plates lose their charge and
48
get precipitated. The particles thus settle down on the floor of the chamber.
The precipitator is called Cottrell precipitator.
SELF EVALUATION
(A) Choose the correct answer :
1. The migration of colloidal particles under the influence of an electric
field is known as
(a) electroosmosis
(b) cataphoresis
(c) electrodialysis
(d) electrophoresis
2. Which one is the correct factor that explains the increase of rate of reaction
by a catalyst
(a) shape selectivity
(b) particle size
(c) increase of free energy
(d) lowering of activation energy
3. Fog is a colloidal solution of
(a) gas in liquid
(c) gas in solid
(b) coagulation
(d) filtration
53
SUMMARY :
Adsorption is a phenomenon of concentration of substance on the surface
of a liquid or solid. The adsorption is classified into physical adsorption and
chemical adsorption.
A catalyst is a substance which alters the speed of a chemical reaction
without itself undergoing any chemical change and the phenomenon is known
as catalysis. Catalytic reactions are classified into homogeneous catalysis
and heterogeneous catalysis. The intermediate compound formation theory
and the adsorption theory are the two main theories which explain the catalytic
processes.
Colloids are intermediate between true solutions and suspensions.
Colloids are classified based on dispersion medium and dispersed phase.
Colloids are prepared by dispersion methods and condensation methods.
Colloids are purified by dialysis, electrodialysis and ultrafiltration. The
properties of colloids are discussed under the types namely, kinetic, optical
and electrical properties.
REFERENCES :
1. A text book of physical chemistry - A.S. Negi and S.C.Anand - Fifth
Print, 1997.
2. Essentials of physical chemistry - B.S. Bahl, G.D.Tuli and Arun-Bahl
- Reprint 2004.
3. Text book of physical chemistry - Louis and Glasstone.
______
54
Electronic conduction
Electrolytic conduction
1.
2.
3.
4.
5.
6.
Semi conductors : Certain type of solids like pure silicon and germanium
A+ + B
For that reason, this theory may be referred to as the theory of electrolytic
dissociations.
2. The ions present in solution constantly reunite to form neutral
molecules. Thus there is a state of equilibrium between the undissociated
molecules and the ions.
AB
A+ + B
Ag+ + NO3
CuSO4
Cu2+ + SO42
H2SO4
2H+ + SO42
positive and negative charges. The total number of cations and anions
produced are equal to those in the formula of the electrolyte.
(e.g.,)
2Al3+ + 3SO42
Al2 (SO4)3
H2O ;
2. The colour of certain salts or their solution is due to the ions present.
For example, copper sulphate is blue due to Cu2+ ions. Nickel salts are
green due to Ni2+ ions. Metallic chromates are yellow due to CrO42
ions.
3. Ostwalds dilution law, common ion effect and solubility product and
other such concepts are based on Arrhenius theory.
4. Chemical reactions between electrolytes are almost ionic reactions. This
is because these are essentially the reaction between oppositely charged
ions. For example,
Ag+ + Cl
AgCl
5. Electrolytic solutions conduct current due to the presence of ions which
migrate in the presence of electric field.
61
CH3COOH
Ka =
[H + ][CH 3COO ]
[CH 3COOH]
Ka =
C .C 2 C
=
C(1 ) 1
a
. Also [H+] = [CH3COO] = C.
C
FK I
=CG J
HCK
a
1/ 2
= (Ka.C)1/2 = K a .C
62
Ka =
Kb =
2 C
is known as the Ostwalds dilution law. For weak bases,
1
b
2 C
and =
at = small values. Kb = dissociation constant
C
1
We know that
Q = It
or
m = Z I t
equivalent mass
g.coulomb-1
96495
equivalent mass
10-3 kg.coulomb-1
96495
Electronic charge.
1 Faraday equal the quantity of electricity produced by 1 mole of
electrons.
Charge of an electron
96495
=
6.023 10
23
Cu(s)
= 0.0592 gm.
Example 2. 0.1978 g of copper is deposited by a current of 0.2 ampere
in 50 minutes. What is the electrichemical equivalent of copper ?
Solution : Here, t = 50 minutes = 50 60 seconds ; I = 0.2 ampere.
Quantity of electricity used is
Q = I t = 0.2 50 60 = 600 coulombs
Amount of copper deposited by 600 coulombs = 0.1978 g
Amount of copper deposited by 1 coulomb =
0.1978
g = 0.0003296 g
600
96,500
10 coulomb
127
I
1 60 60
96,500 10
Q
= 127 60 60
t
= 2.11 ampere.
66
1. 25
x
or
Also,
Eqvt.wt.copper
Eqvt. wt.of Iodine
31.7
,
127
x =
x=
1. 25 127
31. 7
5.0 g of iodine
Wt.of Copper
1.25
=
Wt.of Silver
y
Eqvt.wt.of Cu ( = 31.7)
= Eqvt.wt.of Silver ( =108)
Wt. of silver (y)
108 1.25
31.7
4.26 g
Thus, I =
V
, V = RI, V = Volts, I = ampere, R = ohms
R
and R =
l
a
1 1 l
= .
R a
1
m
= ohm-1.m-1
ohm m2
1
R
l
is called as the cell constant (m-1) and is constant for a given
a
conductance cell.
68
Cell constant
Resistance
1000
N
C =
103
N
mho.m2 gm.equiv.-1
103
mho.m2.(gm.equiv)-1
C
103
mho.m2.mole-1
M
Symbol
Resistance
Resistivity (or)
specific resistance
Conductance
Specific conductivity
(or) specific conductance
Volume (or) dilution
Equivalent conductance
Molar conductance
1
R
V
C
C
Unit
ohm (or)
ohm.m.
ohm-1 (or) Siemen
ohm-1 m-1
m3
ohm-1 m2 (gm.equiv)-1
ohm-1 m2 mole-1
C
Fig. 13.2 Variation of equivalent conductivity C with C for
(a) strong electrolytes and (b) weak electrolytes.
70
l
= 0.88 cm-1
a
Specific conductance =
l
1
a
R
0.88 cm1
V =
1000
= C
4. 23 104 1000
=
0. 04
= 10.575 mho.cm2.eq-1.
C
10.575
= 0.0612 = =
= 172.79 mho.cm2.gm.equiv.-1
Example 3. Equivalent conductivity of acetic acid at infinite dilution
is 39.7 and for 0.1 M acetic acid the equivalent conductance is
5.2 mho.cm2.gm.equiv.-1. Calculate degree of dissociation, H + ion
concentration and dissociation constant of the acid.
C
5. 2
CH3COOH
C (1 )
H+
C
+ CH3COO
C
1
1
+
where +
+ A +
n
m B
= Na+ +
, BaCl2
, AlCl3
= 1 Al3+ + Cl
1 Ba2+
Cl
Cl
1
, Al2(SO4)3 = 1 Al3+ + SO42
2
= + NH4+ + OH
= NH4+ + OH
= NH4+ + Cl + Na+ + OH Na+ Cl
= NH4Cl + NaOH NaCl
+ A+ + B
then = + + +
where and + are the ionic conductances at infinite dilution.
BaCl2 = Ba2+ + 2 Cl
Na2SO4 = 2 Na+ + SO42
Example 4 : Ionic conductances at infinite dilution of Al3+ and SO42
are 189 ohm1 cm2 gm.equiv.-1 and 160 ohm-1 cm2 gm.equiv.-1. Calculate
equivalent and molar conductance of the electrolyte at infinite dilution.
The electrolytes Al2(SO4)3
1
1
Al2(SO4)3 = Al3+ + SO42
3
2
Al2(SO4)3 =
189 160
+
= 63 + 80 = 143 mho cm2 gm.equi1
3
2
74
AB
AgCl(s)
NH4+ + OH
H+ + F
75
HF
( x) ( x )
[H + ][F ]
= (1 x )
[HF]
x2
1. 00
x = (7.2 10-4)1/2
= 2.7 10-2
Thus the degree of dissociation of HF in 1 M solution is 2.7 10-2.
76
2H2O
According to law of mass action,
Keq =
[H 3O+ ][OH ]
[H 2O]2
The constant Kw is called as the ionic product of water and its value is
given by the product of concentrations of hydronium (H3O+) and hydroxide
(OH) ions. At 298 K, Kw = 1 10-14 mol2.dm-6.
The pH of solutions
A knowledge of the concentration of hydrogen ions (more specifically
hydronium ions) is of the greatest importance in chemistry. Hydrogen ion
concentrations are typically quite small numbers. Therefore, chemists report
the hydrogen ion concentration of a solution in terms of pH. It is defined as
the negative of the base-10 logarithm (log) of the H+ concentration.
Mathematically it may be expressed as
pH = log10 [H+]
where [H+] is the concentration of hydrogen ions in moles per litre
Alternative and more useful forms of pH definition are :
1
pH = log [H + ]
and
[H+] = 10pH
77
or
[H+] = 10pH
H+ + OH
78
Since
Kw = 1 10-14 mol2.dm-6.
[H+] = [OH]
acidic solution
basic solution
Expressing the [H+] in terms of pH for the different solutions cited above,
we get what we call the pH scale. On this scale the values range from 0 to
14. Since pH is defined as log [H+] and the hydrogen ion concentration of
water is 10-7, the pH of water is 7. All solutions having pH less than 7 are
acidic and those with pH greater than 7 are basic.
ACID
NEUTRAL
BASE
7
pH < 7
14
pH > 7
The concentrations [H+] and [OH] ions can be calculated from the
expressions :
[H+]
Kw
[OH ]
[OH]
Kw
[H+ ]
= log10 [OH]
pKw
= log10 Kw
Hence, for any aqueous solution at 25oC, pH and pOH add up to 14.00.
That is,
pH + pOH = 14.00
In general, the pH problems may be of the following tpes :
Example 1. The hydrogen ion concentration of a fruit juice is
3.3 10-2 M. What is the pH of the juice ? Is it acidic or basic ?
Solution : The definition of pH is
80
We are given
pOH = 8.5
H+ + Cl.
[H+] from HCl is very much greater than [H+] from water which is
1 107 M.
[H+] =
=
Ka C
1.8 105 0.1 = 1. 8 106
= 1.34 103 M
pH = 2.87
Ba(OH2)
pH = 14 1.4 = 12.6
CH3COOH
Na+
CH3COONa
+ CH3COO
since the salt is completely ionised, it provides the common ions CH3COO
in excess. The common ion effect suppresses the ionisation of acetic acid.
This reduces the concentration of H+ ions which means that pH of the solution
is raised.
It is stated that a buffer solution containing equimolar amounts (0.10 M)
of acetic acid and sodium acetate has pH 4.74. Now we proceed to discuss
how the addition of a small amount of HCl or NaOH to the buffer solution
affects its pH.
The pH of the buffer is governed by the equilibrium
CH3COOH
CH3COO + H+
... (1)
CH3COO
+ Na+
... (2)
84
HA
and
or
Ka
[ H + ][ A ]
=
[ HA ]
[H+] =
[HA]Ka
[A ]
... (1)
The weak acid is only slightly dissociated and its dissociation is further
depressed by the addition of the salt (Na+ A) which provides A ions
(Common ion effect). As a result the equilibrium concentration of the
unionised acid is nearly equal to the initial concentration of the acid. The
equilibrium concentration [A] is presumed to be equal to the initial
concentration of the salt added since it is completely dissociated. Thus we
can write the equation (1) as
[H+] = Ka
[acid ]
[ salt ]
... (2)
where [acid] is the initial concentration of the added acid and [salt] that of
the salt used.
Taking negative logs of both sides of the equation (2), we have
log [H+] = log Ka log
But
log [H+] = pH
85
and
[acid ]
[ salt ]
log Ka = pKa
... (3)
Hence,
pH = pKa log
[acid ]
[ salt ]
= pKa + log
[ salt ]
[acid ]
pH = pKa + log
[ salt ]
[acid ]
[salt]
[base]
[salt] = [acid],
log
[ salt ]
[acid ]
[ salt ]
= log 1 = 0
[acid ]
pKa = pH
The measured pH, therefore, gives the value of pKa of the weak acid.
Likewise we can find the pKb of a weak base by determining the pOH of
equimolar basic buffer.
3. A buffer solution of desired pH can be prepared by adjusting the
concentrations of the salt and the acid added for the buffer.
86
pH = pKa + log
0. 20
0.15
4
pH = 4.7447 + log
3
= 4.7447 + log
[ salt ]
[acid ]
0. 5
0. 5
[C 2 H 5COO ][ H + ] 0. 5 [ H + ]
=
=
[ C 2 H 5COOH ]
0. 5
=
pH =
=
pH =
[H+]
log [H+]
log Ka = log (1.34 105)
4.87
13.10 pH INDICATORS
An indicator is a substance which indicates the completion of a reaction
by sharp colour change at the end point without taking part in the reaction.
The substances which are used to indicate the end point in acid-base reactions
are called as acid-base indicators. (e.g.,) phenolphthalein and methyl orange.
Those substances which change to specific colours in different pH range
values of the medium are called as pH indicators. Incidentally pH indicators
are used as acid-base indicators also.
Selection of pH indicators
Every pH indicator changes its colour specifically in a ranging pH which
is called as indicator range. For some of the indicators, the indicator ranges
are given as below.
Colour of the indicator
Indicator
pH range
Acidic solution
Basic solution
Methyl orange
3.1 - 4.4
Pink
Yellow
Methyl red
4.4 - 6.2
Red
Yellow
Phenol red
6.8 - 8.4
Yellow
Red
8.3 - 10
Colourless
Pink
Phenolphthalein
88
Volume of base
Volume of base
Volume of base
E-end point
H+
Unionised form
(colourless)
Ph
ionised form
(pink)
90
Me+
Unionised form
(yellow)
OH
ionised form
(pink)
benzenoid form
quinonoid form
One form exists in acidic solution and the other form in basic solution.
At least one of the tautomers is a weak acid or a weak base. The two forms
possess two different colours and as the pH of the solution containing the
indicator is changed, the solution shows a change of colour. The colour
change is due to the fact that one tautomer changes over to the other.
For example, phenolphthalein is tautomeric mixture of the two forms.
O
||
C
O
||
C
O
O
OH
C
H+
O
OH
OH
OH
O
||
C
O
C
OH
Quinonoid form, pink,
exists predominant
in basic medium
92
SELF EVALUATION
(A) Choose the correct answer :
1. The process in which chemical change occurs on passing electricity is
termed as ...............
(a) neutralisation
(c) electrolysis
(b) hydrolysis
(d) ionisation
(b) Faraday
(c) Kekule
(d) Avogadro
(b) 0.2
(c) 0.1
(d) 0.3
(b) decreases
(d) becomes zero
2
10. Ostwalds dilution law is applicable in the case of the solution of ...............
(c) NaOH (d) H2SO4
(a) CH3COOH (b) NaCl
11. Which one of the following relationship is correct ?
(a) pH =
1
[H+ ]
1
[ H+ ]
12. When 106 mole of a monobasic strong acid is dissolved in one litre of
solvent, the pH of the solution is ..............
(a) 6
(b) 7
(c) less than 6
(d) more than 7
13. When pH of a solution is 2, the hydrogen ion concentration in moles
litre-1 is .............
(a) 1 1012 (b) 1 102 (c) 1 107 (d) 1 104
14. The pH of a solution containing 0.1 N NaOH solution is ..........
(c) 13
(d) 1013
(a) 1
(b) 101
15. A solution which is resistant to changes of pH on addition of small
amounts of an acid or a base is known as .............
(a) buffer solution
(b) true solution
(c) isohydric solution
(d) ideal solution
16. The hydrogen ion concentration of a buffer solution consisting of a
weak acid and its salt is given by .............
(a) [H+] = Ka
[Acid ]
[Salt ]
[Salt ]
[ Acid ]
7. Define molar, equivalent and specific conductance and describe the effect
of dilution.
8. State and explain Kohlrauschs law.
9. State and explain Debye-Huckel-Onsager equation.
(D) Solve the problems :
1. What is the electrochemical equivalent of a substance when 150 gm of it
is deposited by 10 ampere of current passed for 1 sec ?
[Ans. 15.0]
2. The electrochemical equivalent of an electrolyte is 2.35 gm. amp-1
sec-1. Calculate the amount of the substance deposited when 5 ampere is
passed for 10 sec ?
[Ans. 117.5 gm]
3. To 1 M solution of AgNO3, 0.75 F quantity of current is passed. What is
the concentration of the electrolyte, AgNO3 remaining in the solution ?
4. 0.5 F of electric current was passed though 5 molar solutions of AgNO3,
CuSO4 and AlCl3 connected in series. Find out the concentration of each
of the electrolyte after the electrolysis ?
[Ans. AgNO3, 4.5 M ; CuSO4 ; 4.75 M ; AlCl3 ; 4.839 M]
5. To one molar solution of a trivalent metal salt, electrolysis was carried
out and 0.667 M was the concentration remaining after electrolysis.
Calculate the quantity of electricity passed.
[Ans. 1F]
6. A conductance cell has platinum electrodes, each with 5 cm2 area and
separated by 0.5 cm distance. What is the cell constant?[Ans. 0.1 cm-1]
7. Using a conductivity cell with 0.9 cm-1 cell constant, the conductance
was observed to be 2.5 10-3 mho for 0.07 M KCl solution. What is the
specific conductance of the solution ?
[Ans. 2.25 103 mho.cm-1]
8. Specific conductance of 1 M KNO 3 solution is observed to be
5.55 10-3 mho.cm-1. What is the equivalent conductance of KNO3
when one litre of the solution is used ?[Ans. 5.55 mho.cm2.gm.equiv-1]
9. Explain why on dilution does the conductivity decrease whereas molar
conductivity increases for an electrolytic solution.
96
+ Buffer action, nature of acidic and basic buffers, Henderson equation are
studied.
14. ELECTROCHEMISTRY - II
LEARNING OBJECTIVES
@ Properties and nature of cells will be understood. The differences between
electrolytic and electrochemical cells will be learnt. Interconversion of
electrical and chemical energy will be emphasized.
@ Metal - metal ion electrode and standard hydrogen electrode construction
and the electrode potential will be learnt. Nernst equation will be learnt.
G = nFE and the interconversion of change in free energy and
electrode potentials will be explained.
@ Construction of cells with specific electrodes and the EMF calculations
will be studied. Daniel cell, and its representation, EMF of cell from
two half cell potentials will also be calculated.
@ Complete electrochemical cell representation and writing oxidation and
reduction half cell reactions will be studied with suitable example.
14.1 CELLS
In electrochemistry, the interconversion of chemical energy and electrical
energy is an important aspect that possesses numerous applications. For
example, batteries supply electrical energy stored in the form of chemical
energy for the operation of torch, radio, calculators etc. Conversely, electrical
energy is used to bring about certain chemical reactions which are industrially
important such as purification of metals like copper, aluminium, generation
98
+ Cu2+(aq)
Zn2+(aq) + Cu(s)
Zn(s)
Cu2+
+ 2e
Cu(s)
The decrease in the energy which appears as the heat energy when a
zinc rod is directly dipped into the zinc sulphate solution, is converted into
electrical energy when the same reaction takes place indirectly in an
electrochemical cell. The zinc sulphate is placed in the porous pot while
copper sulphate is placed in a glass vessel.
The Daniel cell is also called as the voltaic cell. However for continuous
supply of current for a long period, the two half cells each comprising the
metal electrode and its aqueous electrolyte kept in separate containers and
can be connected externally as below :
When the cell is set up, electrons flow from zinc electrode through the
wire to the copper cathode. As a result, zinc dissolves in the anode solution
to form Zn2+ ions. The Cu2+ ions in the cathode half cell pick up electrons
and are converted to Cu atoms on the cathode.
Cell Terminology
Before taking up the study of the electrochemical cells, we should be
familiar with a few common terms.
Current is the flow of electrons through a wire or any conductor.
100
Zn
Zn2+
Cu2+
ANODE HALF-CELL
Cu
Phase
Boundary
CATHODE HALF-CELL
101
It may be noted that the metal electrode in anode half-cell is on the left,
while in cathode half-cell it is on the right of the metal ion.
(2) A double vertical line represents the salt bridge, porous partition or
any other means of permitting ion flow while preventing the electrolyte from
mixing.
(3) Anode half-cell is written on the left and cathode half-cell on the
right.
(4) In the complete cell diagram, the two half-cells are separated by a
double vertical line (salt bridge) in between. The zinc-copper cell can now
be written as
Salt
Bridge
Zn
||
Zn2+
Cu2+
ANODE HALF-CELL
Cu
CATHODE HALF-CELL
(5) The symbol for an inert electrode, like the platinum electrode is
often enclosed in a bracket. For example,
Mg
||
Mg2+
H+
ANODE HALF-CELL
Inert
Electrode
H2(Pt)
CATHODE HALF-CELL
(6) The value of emf of a cell is written on the right of the cell diagram.
Thus a zinc-copper cell has emf 1.1 V and is represented as
Zn
ZnSO4
||
CuSO4
Cu
E = + 1.1 V
If the emf acts in the opposite direction through the cell circuit it is
denoted as a negative value.
Cu
CuSO4
||
ZnSO4
Zn
E = 1.1 V
The negative sign also indicates that the cell is not feasible in the given
direction and the reaction will take place in the reverse direction only. The
102
||
Cu2+(aq, 1M)
103
Cu
Eo = 1.10 V
ER E L
Emeasured
(Q EL = 0)
= Emeasured
(Q ER = 0)
Zn2+
||
H+
H2 (1 atm), Pt
The emf of the cell has been found to be 0.76 V which is the emf the
zinc half-cell. Similarly, the emf of the copper electrode, Cu2+ | Cu can be
determined by pairing it with the SHE when the electrochemical cell can be
represented as :
Pt, H2 (1 atm)
H+
||
Cu2+
Cu
The emf of this cell has been determined to be 0.34 V which is the emf
of the copper half-cell.
Eocell = EoCu/Cu2+ EoSHE
= 0.34 Zero
= 0.34 V
The two situations are explained as follows :
When it is placed on the right-hand side of the zinc electrode, the
hydrogen electrode reaction is
2H+ + 2e
H2
H2
+ 2e
The electrons flow to the copper electrode and the hydrogen electrode
105
as the anode. Evidently, the SHE can act both as anode and cathode and,
therefore can be used to determine the emf of any other half-cell electrode
(or single electrode).
According to IUPAC convention, the standard reduction potentials alone
are the standard potentials. The values of the standard potentials at 25oC
(298 K) for some common Reduction Half-reactions are listed in Table below.
Standard Reduction Potentials at 25oC (298K)
Reduction Half - reaction
EoV
2F
2.87
F2 + 2e
H2O2 + 2H+ + 2e
2H2O
1.78
PbSO4 + 2H2O
1.69
Au3+ + 3e
Au
1.50
Cl2 + 2e
2Cl
1.36
Ag+ + e
Ag(s)
0.80
Cu2+ + 2e
Cu(s)
0.34
2 H+ + 2e
H2(g)
0.00
Pb2+ + 2e
Pb(s)
0.13
Zn2+ + 2e
Zn(s)
0.76
Zn2+(aq)
||
Ag+(aq)
106
Ag
In general, if
+ Zn2+(aq)
2Ag+(aq) + Zn(s)
is feasible or not.
Solution : The cell half reactions are
Anode
Cathode :
2Ag(s)
2Ag+(aq) + 2e
Eo = 0.80 V
Zn2+(aq) + 2e
Zn(s)
Eo = 0.763 V
2Al3+ + 3Sn2+(aq)
107
Anode
Cathode :
2Al3+ + 6e
2Al(g)
3Sn4+ + 6e
3Sn2+
Eo = 1.66 V
Eo = + 0.15 V
= 1.81 V
Since Eocell is positive, the reaction is feasible.
Metal displacement : (Predicting whether a metal will displace
another metal from its salt solution or not).
As already shown, the metals near the bottom of the electrochemical
series are strong reducing agents and are themselves oxidised to metal ions.
On the contrary, the metal lying higher up in the series are strong oxidising
agents and their ions are readily reduced to the metal itself. For example,
zinc lying down below the series is oxidised to Zn2+ ion, while copper which
is higher up in the series is produced by reduction of Cu2+ ion.
Zn2+ + 2e
Zn
Cu2+
Cu
+ 2e
Zn2+ + H2
Cu2+ + H2
108
Example 1 : Calculate the standard e.m.f. of the cell : Cd, Cd2+ || Cu2+,
Cu and determine the cell reaction. The standard reduction potentials of
Cu2+, Cu and Cd2+, Cd are 0.34V and 0.40 volts respectively. Predict the
feasibility of the cell reaction.
Eocell = Standard EMF of the cell
= Eoright Eoleft
= [Std. reduction potential of Cu2+, Cu]
[Std. reduction potentials of Cd2+, Cd]
= EoCu2+,Cu EoCd2+,Cd
= 0.34 V ( 0.4 V)
= + 0.74 Volts.
Left hand electrode (oxidation half cell) reaction is
Cd2+ + 2e
Cd(s)
Right hand electrode (reduction half cell) reaction is
Cu2+ + 2e
Cu(s)
The cell reaction is
Cd2+(aq) + Cu(s)
Cd(s) + Cu2+(aq)
Eocell is positive. The cell reaction is feasible.
Example 2 : Determine the standard emf of the cell and predict its
feasibility.
Ag, Ag+ || H+, H2(g)1atm, Pt.
The standard reduction potential of Ag+, Ag is 0.80 volts.
The right hand side electrode is SHE.
Eocell = EoRight EoLeft
Eocell = [Std. reduction potential of SHE]
[Std. reduction potential of Ag+, Ag]
= 0 (+ 0.8 V) = 0.8 Volts.
Since Eocell is negative, the cell reaction is not feasible.
109
... (1)
... (2)
... (3)
Thus only when E has a positive value, G value will be negative and
the cell reaction will be spontaneous and the e.m.f. of the cell can be measured.
Here E refers to the Ecell.
Thus, the electrical energy supplied by the cell is (nFE) equal to the free
energy decrease (G) of the cell reaction occurring in the cell.
Example : Determine the standard emf of the cell and standard free
energy change of the cell reaction.
Zn, Zn2+ || Ni2+, Ni. The standard reduction potentials of Zn2+, Zn and
Ni2+, Ni half cells are 0.76 V and 0.25 V respectively.
Eocell =
=
Go =
n FEocell
2 electrons
Go =
C +
G = Go RT ln a a
A
B
If E is the E.M.F. of the cell in volts and the cell reaction involves the
passage of n faradays (i.e.,) nF coulombs, the electrical work done by the
cell is in nFE volt-coulombs or Joules. Hence free energy decrease of the
system, G, is given by the expression
G = nFE
aC aD
nFE = Go RT ln a a
A
B
aC aD
= nFEo RT ln a a
A
B
E = Eo
aC aD
RT
ln a a
nF
A
B
111
aC aD
RT
ln a a is often referred to as the Nernst equation
nF
A
B
[C] [D]
RT
ln [A][B]
nF
RT
ln K.
nF
RT
log K,
nF
Mn+ + ne
112
...(1)
[M n+ ]
2. 303 RT
log
... (2)
[M]
nF
The activity of solid metal [M] is equal to unity. Therefore, the Nernst
equation can be written as
E = Eo
2. 303 RT
log [Mn+]... (3)
nF
0. 0591
log [Mn+]
n
... (4)
Zn
Eo
0. 0591
log [Zn2+]
n
0. 0591
(2)
2
0.763
Ecell =
0. 0591
log K
n
2Ag+ + 2e
Anode
Zn
Cell
Zn + 2Ag+
2Ag
Eo = + 0.80
Zn2+ + 2e
Eo = 0.76 V
Zn2+ + 2Ag
Eo = 1.56 V
[Zn2 + ]
Step 2. K for the cell reaction =
[Ag + ]2
Substituting the given values in the Nernst equation and solving for
Ecell, we have
Eocell
Ecell =
0. 0591
log K
n
[Zn2 + ]
0. 0591
1.56
log
[Ag + ]2
2
[103 ]
0. 0591
1.56
log
[101 ]2
2
=
=
=
= Eocell
log K =
0. 0591
log K
n
n Eocell
0. 0591
Zn2+ + 2Ag
Eocell = 1.56 V
n Eocell
0. 0591
6.19 1052
Example 4 : Calculate the E.M.F. of the zinc - silver cell at 25oC when
[Zn2+] = 0.10 M and [Ag+] = 10 M. (Eo cell at 25oC = 1.56 volt]
Solution : The cell reaction in the zinc - silver cell would be
2Ag+ + Zn
2Ag + Zn2+
The Nernst equation for the above all reaction may be written as :
115
Ecell =
Eocell
[Ag]2 [Zn2 + ]
RT
ln
[Ag + ]2 [Zn]
nF
Eo
[Zn2 + ]
cell ln [Ag + ]2
1.56
log
0.1
(10)2
1.648 volts.
ZnO22 + 2H2O
HgO(s) + H2O + 2e
Hg(s) + 2OH
Cell reaction is
ZnO22 + Hg(s) + H2O
PbSO4(s) + 2e
PbSO4(s) + 2H2O
Cell reaction is
Pb(s) + PbO2(s) + 4H+ + 2SO42
2PbSO4(s) + 2H2O
116
H2(g)
Hg2Cl2(s) + 2e
2Hg(l) + 2Cl
Hg2Cl2(s) + H2
Zn2+ (a = 0.1) + Cu
Eocell
aZn 2 + aCu
RT
ln
aZn aCu2 +
2F
Eocell
aZn 2+
RT
ln a 2+
2F
Cu
Eocell
Ecell
1.099
0. 0591
0.1
log
2
0. 01
1.099
0. 0591
log 10
2
1.099 0.02956
1.0694 V
117
212.1 kJ/mol.
Fe3+ + e
Fe2+ and Fe2+ + 2e
0.44 V respectively.
Fe2+
Fe(s)
Fe(s).
Ag+ + Fe2+
Ag(s)
At cathode :
Fe3+ + e
Ag+ + e
Fe2+
Fe2+ + Ag+
aAg + aFe 2+
aFe 3+
aAg + aFe 2+
aFe 3+
0. 0591
log Keq
n
0. 0281 1
SELF EVALUATION
(A) Choose the correct answer :
1. The potential of a single electrode is a half cell is called the
(a) Reduction potential
(b) Half-wave potential
(c) Single electrode potential (d) cell potential
2. The relationship between free energy change and e.m.f. of a cell is
(a) G = nFE (b) H = nFE (c) E = nFG
(d) F = nEG
3. The feasibility of a redox reaction can be predicted with the help of
(a) Electronegativity
(b) Electrochemical series
(c) Electron affinity
(d) Equivalent conductance
4. The metals near the bottom of the electrochemical series are
(a) strong reducing agents
(b) strong oxidising agents
(c) weak reducing agents
(d) weak oxidising agents
5. The emf of a cell with 1 M solutions of reactants and products in solution
at 25o C is called
(a) Half cell potential
(b) Standard emf
(c) Single electrode potential (d) Redox potential
6. The relationship between equilibrium constant and standard emf of a
cell is
(a) Eo = 0.0591 log K
(b) 0.0591 E o = log K
o
(d) nEo = 0.0591 log K
(c) nE = 0.0951 log K
119
2Ag(s) + Zn(NO3)2.
Sn2+
2F
120
1
0. 0591
log
]
[Cu2+ ]
2
3E1 E2
]
2
7. Calculate the standard emf of the cell having the standard free energy
change of the cell reaction is 64.84 kJ for 2 electrons transfer.
[Ans. Eo = 0.336 V]
8. Calculate the emf of the cell Zn/ZnO2, OH(aq), HgO/Hg given that Eo
values of OH, ZnO2 / Zn and OH, HgO/Hg half cells are 1.216 V
and 0.098 V respectively.
[Hint : Eo = EoR EoL ; Eo = 1.314V]
9. The equilibrium constant of cell reaction :
Fe2+ + Ag+ is 0.335, at 25oC. Calculate the standard
Ag(s) + Fe3+
emf of the cell Ag/Ag+ ; Fe3+, Fe2+ / Pt. Calculate Eo of half cell Fe 3+,
Fe2+/Pt if Eo of half cell Ag+/Ag is 0.7991V. Calculate Eo of Fe3+, Fe2+/
Pt half cell.
[Ans. EoFe3+/Fe2+ = 0.771V]
10. Calculate the emf of the cell having the cell reaction
2Ag+ + Zn
2Ag + Zn2+ and Eocell = 1.56 V at 25oC when
concentration of Zn2+ = 0.1 M and Ag+ = 10 M in the solution.
[Hint : Ecell =
Eocell
[Zn2 + ]
RT
n F ln
[Ag + ]2
121
[Ans. 1.648 V]
122
CH3
CH3
I CH3
H
Cis isomer
H3C II H
Trans isomer
123
The isomer in which similar groups lie on the same side is called cis
isomer (I). The other in which similar groups lie in opposite direction is
called Trans isomer (II). This isomerism is called Cis-Trans isomerism.
The two groups attached to the carbon atoms need not be same, it may
be different also. e.g.,
2-pentene
CH2CH3
CH2CH3
C
H
C
CH3
H3C
Cis
H
Trans
This isomerism arises out of the hindrance to rotation about the C=C
bond in such molecules.
The cis-trans isomers do not differ much in chemical properties. They
differ in physical properties like boiling point, melting point, crystal structure,
solubility and refractive index. Highly substituted olefin is more stable than
less substituted olefin. Among substituted olefins, trans olefin is more stable
than cis olefin. In the cis isomer because similar groups are very near each
other, Vander Waals repulsion and steric hindrance make the molecule much
unstable. In the trans isomer, similar groups are diagonally opposite to each
other. Hence there is no such steric interaction. Generally trans isomer is
more stable than cis isomer. Hence reactivity of cis isomer may be little
higher than the trans isomer. The energy of the cis isomer is greater than that
of trans isomer.
Though at room temperature, cis and trans isomers are stable and are
not interconvertible, on heating to a certain temperature, trans isomer can
be converted to cis isomer and vice-versa. Breaking of carbon-carbon
-bond and its reformation is responsible for the interconversion.
Trans isomer
Cis isomer
COOH
COOH
COOH
HOOC
Cis
[Maleic acid]
Trans
[Fumaric acid]
H3C
H
C
C
H3CCH2
CH3
A newer system based on the priority of groups is the Cahn-IngoldPrelog convention. This system is called the (E-Z) system, applies to alkene
diastereomers of all type. If the two groups of higher priority are on the
same side of the double bond, the alkene is designated Z (from the German
word Zusammen-meaning together). If the two groups of high priority are
on opposite sides of the double bond, the alkene is designated E (from the
German, entgegen, meaning opposite)
The priorities follow the order of decreasing atomic number of the atom
directly bonded to the carbon.
For some compounds the priority is shown by numbers as
1
H3C
H3C
C
Z-isomer
E-isomer
C
H3CCH2
1
C
CH3
2
H3CCH2
2
125
CH2CH2CH3
1
H3C
H3C
Cl
C
E-isomer
Z-isomer
Cl
CH2CH3
1
Dipolemoment studies is one of the best methods of identifying cistrans isomers. Generally cis isomers have larger dipolemoment than trans
isomers. Often DPM of trans isomer is zero. e.g., Trans 2-butene and Trans
2,3-dibromo-2-butene. (Refer Chapter on disubstituted benzene)
1,3 - butadiene
CH2=CHCH=CH2
This molecule can exist in two forms.
CH2 = CH
|
CH = CH2
and
I
CH2 = CH
|
CH2 = CH
II
Though these two forms do not differ very much in their energy and
stability, the (I) form, which is similar to trans is more stable than (II) form
which is similar to cis. These two forms do not arise out of the hindrance
to rotation about C=C, instead the restricted rotation about CC. In order
to indicate that, this cis-trans isomerism is due to restricted rotation about
CC bond, they are named as,
S-trans
S-cis
126
H
H
H
H
H
H
H
H
H
H
Cyclopropane
[Planar conformation]
Cyclo butane
[non planar conformation]
Cyclo pentane
[non planar conformation]
Cyclohexane :
As early as 1890, Sachse suggested that cyclohexane ring exists in two
non planar forms (i.e.,) boat and chair conformations. The energy difference
between these two forms was found to be only 6.5 K.cal/mole by Pitzer. The
energy difference is small enough for interconversion to take place.
127
Both the boat form and chair form are free of angle strain called Baeyers
strain (i.e., the valence bond angle is 109o28']
a
x
Chair conformation
Boat conformation
a = axial, e = equatorial
f = flagpole, s = bowspirit,
x-x = pair of eclipsing hydrogen atoms
Chair conformation :
There are two types of CH bonds.
Types of CH bonds
Axial
[Six CH bonds parallel
to the axis of the
molecule]
Equatorial
[Six CH bonds subtending
an angle of about 70o
and 110o with the axis
3-axial bonds
facing upward
-axial
3-equatorial
bonds facing
upward
-equatorial
3-axial bonds
facing downward
-axial
3-equatorial
bonds facing
downward
-equatorial
Every pair of carbon atoms (Two carbon atoms directly bonded to each
other) in chair form exists in skew form.
Boat conformation
This form has two pairs of carbon atoms with eclipsing bonds. This
eclipsing interaction destabilies boat form.
Though the chair form is stable, it is sufficiently flexible to turn itself
upside down called ring flipping so that all bonds which are axial originally
become equatorial and vice versa.
128
R
H
H
H
There exists an equilibrium between these two chair forms with boat
form as intermediate.
A mono substituted cyclohexane like cyclohexanol exists in the two
chair forms. These two forms are interconvertible and exist in equilibrium.
OH
OH
I
II
In one form (I) the OH group is axially oriented. In the other form (II)
the OH group is equatorially oriented. The energy of the axial conformer is
little higher than that of the equatorial conformer. Because the axial
substituent experiences steric interaction with the axial H-atoms present at
the third carbon atoms. This decreases the stability of the axial conformer.
This is called 1 : 3-diaxial interaction. This interaction is absent in the
equatorial conformer. Hence equatorial cyclohexanol is present to an extent
of about 90% in the equilibrium mixture. The axial isomer is present only to
10%.
Energy level diagram for axial and equatorial alcohols
Boat
11 KCals
Axial
0.7 KCal
Equatorial
129
Nicol
prism
or
p-p light
Sample
Clockwise
direction
Anti-Clockwise
direction
CH3CHDOH
CH3
CH3
C
H
(ethanol-symmetric
molecule)
C
OH
OH
H
CH3
OH
D
e.g.,
H
C*
COOH
HO
CH3
R
H
C*
H2N
-amino acid
OH
HO
COOH
COOH
COOH
Optical isomers :
Chiral molecules can have two different configurations. Each
configuration stands for one optical isomer. Thus dextrorotatory isomer has
configuration which is the mirror image of the laevorotatory isomer. Such
optical isomers which differ only in the sign of (or direction of) optical rotation
are called enantiomers.
132
When equal amounts of d-isomer and l-isomer are mixed one gets a
racemic mixture and this process is called racemisation. A racemic mixture
becomes optically inactive. Because, in this mixture rotation towards
clockwise direction by the dextro isomers is compensated by the rotation
towards the anticlockwise direction by the laevo isomers. The optical
inactivity of a racemic mixture is said to be due to external compensation.
Any how an optically inactive racemic form can be separated into two active
forms. This process of separation is called resolution of the racemic
mixture.
A molecule with more than one chiral carbon
A molecule can have more than one chiral centres. Correspondingly the
number of isomers is increased. In general for a molecule with n-different
chiral centres, 2n-isomers are possible. A molecule can have more than one
identical asymmetric carbon atoms. (e.g.,) butane -2,3-diol and tartaric acid.
CH3
H
COOH
OH
HO
OH
HO
CH3
COOH
Diol
Tartaric acid
OH
HO
HO
COOH
OH
COOH
The enantiomers of tartaric acid, have the same magnitude but different
sign of optical rotation. They have object-mirror image relationship.
In the d-isomer, each of the two asymmetric carbon atoms rotate the
plane of the polarised light towards right leading to overall dextro rotation.
In the same way in the l - isomer, the overall rotation is laevo.
There is another optical isomer for tartaric acid in which one asymmetric
carbon atom is dextrorotatory and the other laevorotatory-both rotating to
the same extent in opposite directions. The net result is, that this isomer
becomes optically inactive and is called the Meso isomer.
COOH
H
OH
OH
COOH
Though the Meso isomer has two asymmetric carbon atoms the
configuration of one carbon is the mirror image of the other, the net result
being the molecule as a whole becomes symmetric. This molecule is said to
have a symmetric plane, which divides the molecule into two equal halves.
The molecule becomes achiral. It has configuration which is superimposable on its mirror image.
The optical inactivity of the Meso isomer is due to the internal
compensation. It is due to the inherent symmetry in the molecule. Mesoform
cannot be separated into optically active enantiomeric pairs. This form is a
single substance and not a mixture.
Racemic form
Meso form
3. Molecules of isomers
present are chiral.
When equal amounts of d-tartaric acid and l-tartaric acid are mixed, we
get racemic tartaric acid which is an optically inactive mixture. This can be
separated into two optically active forms.
d- and l-isomers have the same magnitude but different sign of optical
rotation, hence they are called enantiomers. The Meso tartaric acid differs in
the magnitude of optical rotation from the d- or l- isomer. Hence Mesoform
is said to be a diastereomer of the active form.
Enantiomer
Diastereomer
1. Optical isomers having the same
magnitude but different sign of
optical rotation.
2. They have configuration with
non-super imposable object mirror
image relationship.
3. Enantiomers are identical in all
properties except the sign of
optical rotation.
4. Separation of enantiomers is a
tedious process.
CHO
OH
CH2OH
CH2OH
HO
l or () glyceraldehyde
L
135
In general more oxidised group is shown at the top and the reduced
group at the bottom. The chiral molecule is viewed in such a way that H, Xlie above the plane of the paper and R1, R2-lie below the plane of the paper.
The D, L-configurations are shown as :
R2
R2
R1
R1
R2
C*
C*
H
R1
R1
COOH
OH
HO
CH3
CH3
L
136
and tartaric acid - (R-stands for the remaining half portion of the molecule)
COOH
H
OH
HO
D-configuration
COOH
HO
OH
H
COOH
COOH
HO
COOH
R = CH(OH)COOH
R
H
L-configuration
COOH
OH
HO
OH
COOH
COOH
HO
Exchange
H by OH
R
OH
COOH
Exchange
H by COOH
COOH
OH
COOH
II
X
X
X
X = any substituent
These are three distinct forms differing in many properties though they
have the same formula. Hence they are said to exhibit isomerism. In these
three structures the isomers differ in the relative position of the substitutents.
Hence they are called position isomers.
When the substituents are in adjacent positions in the benzene ring, it is
called ortho isomer.
When the two substituents are exactly opposite to each other, it is a
para isomer.
When the angle between two substituents is 120o. It is a meta isomer.
Example,
Cl
Cl
Cl
Cl
Cl
Cl
Ortho dichloro
benzene
Meta dichloro
benzene
Para-dichloro
benzene
Isomers can also be named using the number of the carbon atom thus
Ortho isomer
is
1,2-dichloro benzene
Meta isomer
is
1,3-dichloro benzene
Para isomer
is
1,4-dichloro benzene
138
It should be remembered that there are two ortho and two meta and
only one para position to the substituent already present in a molecule of
benzene.
Cl
Cl
CH3
Cl
Cl
CH3
O2N
NO2
and
(OR)
and
These two are identical and are not isomers. Similarly the following two
represent one and the same compound and are not non-superimposable mirror
images.
Cl
Cl
Cl
and
Cl
CH3
(OR)
CH3
NO2
and
O2N
Ortho, meta and para isomers differ mainly in physical properties like
melting point, refractive index, solubility. Their behaviour under an applied
electric field differs widely. This behaviour is measured by a quantity called
Dipole moment. For disubstituted benzenes the magnitude of DPM depends
on the angle between the two substituents. For example, for dichloro benzene.
Cl
Cl
Cl
Cl
Cl
Cl
angle = 60o
= 120o
= 180o
SELF EVALUATION
Choose the correct answer :
1. Identify chiral molecule among the following :
(a) isopropyl alcohol
(b) isobutyl alcohol
(c) 2-pentanol
(d) 1-bromo-3-butene
2. Which among the following is not having an asymmetric carbon atom ?
(a) 2-chloro butane
(b) 2-bromo-3-butene
(c) 2-hydroxy propanal
(d) isobutyric acid
3. Which among the following can be a chiral center ?
(a) C+ of a cabocation
(b) carbon of a radical
2
(c) an sp carbon
(d) an sp3 carbon
4. Give the structural formulae for the simplest chiral.
(a) alkane
(b) alkene
(c) alkyne (d) alcohol
(e) aldehyde
(f) ketone
(g) carboxylic acid (h) amine.
GEOMETRICAL ISOMERISM
1. Which among the following exhibit geometrical isomerism ?
(a) isobutyraldehyde
(b) 1-butene
(c) 1,1-dichloro ethylene
(d) 1-chloro-2-bromo ethylene
2. Which among the following does not exhibit geometrical isomerism ?
(b) CH2Br
(a) CH3CH=CHBr
CH2I
C=C
H3C
CH2Br
CH3
CH2CH3
(b) BrCH
2
C=C
H
CH3
C=C
H3C
140
CH2CH3
CH3
(c)
(d)
C=C
Cl
H
C=C
Br
Br
5. How many linear chain isomers are possible for each of the following
olefins ?
Practice Questions
(a) C4H8
(b) C5H10
(c) C3H6
(d) C6H12
6. Draw the cis, trans isomers for the following and designate them as E or Z.
(a) HOH2CCH = CHCH2CH3 (b) CH3CH=CHCO2H
(c) CH3CH = CH CHO
(d) CHCl = CHBr
7. Identify each of the following alkenes as being either cis or trans.
ClCH2
(a)
Cl
C=C
OHC
H
C=C
(c)
Cl
(b)
C=C
H
COOH
(d)
CHO
Br
C=C
H
COOH
CH2OH
CH3
C
(a)
C=C
(b)
C
CHO
C=C
CH3
COOH
HOCH2
(c)
Cl
(d)
CH2Cl
H
C=C
Br
1. (b) CH3CH2CH2CH(OH)CH3
2. (d)
CH3
|
CH3CHCOOH
CH3
|
CH3CH2CH CCH
CH3
H
C=C
H3C
C2H5
143
3. (a) Z
_____
145
ethyl alcohol
allyl alcohol
benzyl alcohol
A compound can have more than one hydroxy group such as ethylene
glycol, a dihydric alcohol and
CH2 CH2
|
|
OH
OH
Glycerol a trihydric alcohol.
CH2 CH CH2
|
|
|
OH OH OH
R
R CH2OH
CHOH
R
Primary
1o
Secondary
2o
R
R
R
COH
Tertiary
3o
Common
name
Carbinol
name
CH3CH2OH
ethyl alcohol
methyl carbinol
ethanol
CH3CH2CH2OH
n-propyl alcohol
ethyl carbinol
1-propanol
CH3CHOHCH3
isopropyl alcohol
dimethyl carbinol
2-propanol
CH3CH2CHOH
|
CH3
secondary butyl
alcohol
ethyl methyl
carbinol
2-butanol
148
IUPAC
name
CH3CHCH2OH
|
CH3
Isobutyl alcohol
isopropyl carbinol
2-methyl1-propanol
CH3
|
H3CCOH
|
CH3
tert-butyl alcohol
trimethyl carbinol
2-methyl2-propanol
C6H5CH2OH
Benzyl alcohol
phenyl carbinol
phenyl methanol
CH3CH2CHOHCH2CH2CH3
---
CH3 CH3
|
|
CH3 C C CH3
|
|
H OH
----
dimethyl isopropyl
carbinol
2,3- dimethy1-2
butanol
2-methyl-1-propanol
(branched chain)
CH3CH2CH2CHOHCH3
3-pentanol
2-pentanol
CH3CH2CH2CH2CH2OH
1-pentanol
3. Functional isomerism :
Alcohols are isomeric with ethers, having the same formula with different
functional groups.
CH3CH2CH2OH
CH3OCH2CH3
n-propyl alcohol
149
H2SO4
propylene
H+
R CH CH3
H2O
OH2
|
R CH CH3
H+
OH
|
RCHCH3
Simple alcohol (C2H5OH) can be prepared by absorbing olefin in con.
H2SO4 with the formation of ethyl hydrogen sulphate, which undergoes
hydrolysis to give alcohol.
C2H4 + H2SO4
353K
C2H5 HSO4
HOC2H5 + H2SO4
150
H
C=O
H OH
R CO MgX
RCH2OH + Mg
OH
H2/Pt
R
RCH2OH ;
C=O
H2/Pt
R2CHOH
LiAlH4
R
CH2 ;
C=O
HO
NaBH4
R
CHOH
R
H2O
RX + AgOH
ROH + NaX
ROH + AgX
(b) Aliphatic primary amines react with Nitrous acid forming alcohols.
Diazonium ion is formed as an intermediate.
RNH2 + HONO
H2O
[RN=N+]
unstable
151
H2O
N2 + ROH
H+
R'COOH + ROH
OH
R'COOR + NaOH
R'COONa + ROH
ROR + HI
RO R
|
H
ROH + RI
H2SO4
HO
2
C2H5OC2H5
2C2H5OH + H+
|
H
Protonation of ether oxygen, followed by nucleophilic displacement of
ethyl alcohol by water.
C2H5OC2H5 + H2O
HOH
ROH
Hence alcohol contains alkane like alkyl group and water like hydroxyl
group. The OH group gives the alcohol its characteristic properties and the
alkyl group modifies it.
152
R
H
|
|
OH .....OH
Mol.wt.
Boiling point. K
CH3OH
32
333
CH3CH3
30
184.4
C2H5OH
46
351.5
C3H8
44
228.5
Chemical Properties
Alcohols can be considered to be derived from alkane as well as water.
CH3H
CH3OH
HOH
Methane
Methanol
Water
m.p
89 K
176.8 K
273 K
b.p
159 K
338 K
373 K
Solubility
in water
insoluble
in water
soluble
in water and
slightly soluble
in hydro carbon.
insoluble in
hydro
carbon
Similar to water forming hydrate with salts, lower alcohols also form
addition compounds with salts (e.g.,) CaCl2.4C2H5OH, MgCl2. 6CH3OH
In chemical reactions also alcohols bear striking resemblance to water
and alkane.
Properties due to the acidic nature of hydrogen of the OH group.
1. Alcohols are weaker acid than water because of +I effect of alkyl
groups. Hence alcohols react only with electro positive metals evolving
hydrogen.
ROH + Na
RONa + H2
(Sodium alkoxide)
2C2H5OH + 2Na
2C2H5ONa + H2
(Sodium ethoxide)
The acid strength decreases in the order 1o > 2o > 3o because of the
electron releasing effect of the alkyl groups.
2. Strongly basic substances like organometallic compounds are
decomposed by alcohol.
ROH + CH3MgBr
ROMgBr + CH4
154
ROH
H
|
ROCOR'
+
R'COCl
Cl
H+
ROCOR'
H
|
R O COR' + R' COO()
+
COR'
ROH +
O
COR'
H+
H+ + ROCOR'
Reactions in which the OH group is involved.
1. Alcohols react with carboxylic acids in presence of con. sulphuric
acid. Alcohol molecule brings forth a nucleophilic attack on the carbonyl
carbon to form ester.
O
||
H+
ROH
+
H
OCR'
ROCOR' + H2O
..
C2H5OH + CH3COOH
H+
CH3COOC2H5 + H2O
(ethyl acetate)
ZnCl2
155
RCl + H2O
(CH3)3 COH
3o alcohol
anhyd. ZnCl 2
con.HCl
(CH3)2 CHOH
anhyd. ZnCl2
2o alcohol
(CH3)2CHCl + H2O
CH3CH2OH
1o alcohol
anhydrous ZnCl2
CH3CH2Cl + H2O
(No turbidity appears easily)
but only on heating
RCH2OH + SOCl2
RCH2OSOCl
156
RCH2OSO Cl
RCH2Cl + SO2
3C2H5OH + PCl3
3C2H5Cl + H3PO3
RCH2OH + PCl5
RCH2 O
Cl()
PCl4
+
RCH2 O
Cl
5. Dehydration
(a) Alcohols undergo intermolecular dehydration by treating with
con. H2SO4 acid to give ethers. In the first step alkyl hydrogen sulphate is formed
which with excess alcohols undergoes nucleophilic displacement reaction.
C2H5OH + H2SO4
410K
C2H5 HSO4
C2H5 O
+
C2H5
C2H5OH
157
HSO4
H
+
C2H5 O
C2H5OC2H5
H+
C2H5
(b) Intramolecular dehydration takes place leading to the formation of
olefins. This reaction involves -elimination. It is E1 reaction and the
intermediate is carbonium ion.
(CH3)3 COH
H+
(CH3)3 C
(CH3)3 C+
(CH3)2 C = CH2
H2O
+
H+
CH2=CH2 +
H2SO4
Thus ethyl alcohol gives ethylene on treating with excess con. H 2SO4
acid at 440 K.
(c) Dehydration can also be carried out by passing the alcohol vapour
over alumina at 620 K.
CH3CH2OH
Al2O3
620 K
CH2=CH2
ROH
NH3
Al2O3
633 K
RNH2
ROH
158
R2NH
ROH
R3N
H2O
CH3CH=O
CH3COOH
aldehyde
(primary alcohol)
CH3
|
CH3 C O
| |
H H
(O)
H2O
CH3
|
CH3C=O
(Ketone)
(O)
CH3COOH
(secondary alcohol)
CH3
|
H3C C OH
|
CH3
H+
CH3
|
CH3 C = CH2
(tertiary alcohol)
(O)
CH3COCH3 + HCOOH
CH3COOH
CH3CH2OH
(O)
CH3CHO
CH3COOH
The breath analysis test for the detection of ethanol involves the oxidation
of alcohol in the breath of a person who has consumed alcohol, by acidic
potassium dichromate and observing the change in the colour of the chromium
ion (CrVI) from yellow orange to Cr(III) which is blue green colour.
2. Reaction with chlorine water
When alcohols are treated with chlorine water, or sodium hypochlorite
or bleaching powder solution, they are oxidised.
Primary alcohols are oxidised to aldehydes
(O)
CH3CH2OH
Ethyl alcohol
CH3CHO
H2O
H2O
Acetaldehyde
CH3
(O)
CO
CH3
CH3
Isopropyl alcohol
Acetone
Tertiary alcohols do not undergo this reaction because it does not contain
-hydrogen which is involved.
The carbonyl compounds formed undergo further chlorination forming
chlorinated aldehydes and ketones.
CH3CHO
CH3COCH3
Cl2
Cl2
160
I2/KOH
CH3CHO
I2/KOH
CH3CHOHCH3
I2
CH3COCH3
KOH
CI3CHO
I2
CI3COCH3
CHI3 + HCOOK
KOH
CHI3 + CH3COOK
Cu/573K
CH3CHO
H2
CH3
|
CH3 C = O
H2
(aldehyde)
Primary alcohol
CH3
|
CH3 C O
|
|
H H
Cu/573 K
(acetone)
Secondary alcohol
CH3
OH
C
CH3
CH3
CH3
Cu/573K
C=CH2
dehydration
H2O
CH3
Tertiary alcohol
Isobutylene
(c) The nitro alkane is treated with Nitrous acid (HNO2) and then with
aqueous KOH.
The alcohols are identified from the colour of the product.
(a) Primary alcohol:
P/I2
CH3CH2OH
CH3CH2I
primary alcohol
KOH
CH3 C=NOH
|
NO2
(Nitroxime or nitrolic acid)
AgNO2
CH3C=NOK+
|
NO2
CH3
P/I2
CHOH
CHI
CH3
CH3
Secondary alcohol
CH3
NO2
CH3
NO2
C
CH3
+ HON=O
H
KOH
C
CH3
AgNO2
N=O
(Pseudo nitrol)
blue colour
CH3
P/I2
CH3
AgNO2
CH3 C I
CH3 C NO2
H3C
HNO2
No reaction
CH3
Nitro compound
colourless
USES OF ALCOHOLS
(a) Methyl alcohol is used as an industrial solvent (b) as an antifreeze in
automobile radiators, (c) for the manufacture of formaldehyde.
Methanol is poisonous in nature and when taken orally can cause
blindness and even death. Ethanol which contains 5% methanol is known as
methylated or denatured spirit. It is used as a fuel in spirit lamp and as a
solvent for wood polish, methanol is used as a motor fuel along with petrol.
Ethyl alcohol one of the most extensively used organic compound (a) in
alcoholic beverage, (b) industrial solvent, (c) in pharmaceutical preparation,
(d) as a preservative for biological specimens, (e) in the preparation of large
number of other organic compounds like ether, iodoform, acetaldehyde etc.,
and (f) as a good solvent for recrystallisation and extraction of plant materials
etc.
16.4 DIHYDRIC ALCOHOLS
Compounds having two hydroxyl groups are known as dihydric alcohols
or diols. If two hydroxyl groups are linked to the same carbon atom, it is
called gem diols. These are unstable. The relative position of the two
hydroxyl groups can be 1, 2 or 1, 3 or 1, 4 and so on.
Example,
OH
|
CH3 C OH
|
H
CH3 C = O
|
H
+ H2O
Gemdiol
CH2OH
|
CH2OH
CH2OH
|
CH2
|
CH2OH
Nomenclature of 1,2-diols
1. In the common system, the name is arrived at by adding the word
glycol to the name of the olefin from which it is derived.
163
HOCH2 CH2OH
CH3CH(OH)CH2OH
ethylene glycol
propylene glycol
2. In the IUPAC system, the suffix diol is added to the name of parent
alkane.
HOCH2 CH2OH
CH3CH(OH)CH2OH
ethane-1,2-diol
propane-1,2-diol
ISOMERISM
Position Isomerism
Diols having the same molecular formula differ in the position of the
hydroxyl groups.
CH3CH(OH)CH2OH
CH2(OH)CH2CH2OH
propane-1,2-diol
propane 1,3-diol
Functional Isomerism
Diols are isomeric with ethers or hydroxy ethers.
CH3CH(OH)CH2OH is isomeric with
CH3OCH2OCH3
and CH3OCH2CH2OH
Dimethoxy methane
2-methoxy-ethanol
RCHOH CH2OH
RCHCH2
O
164
H3O+
R CH CH2
|
|
OH OH
CH2 = CH2 + O2
CH2 CH2
473-673 K
O
This is hydrolysed to ethylene glycol by dil. HCl or sulphuric acid at
333 K.
CH2 CH2
H3O+
CH2OH CH2OH
O
This reaction proceeds via the nucleophilic attack by water on the
protonated epoxide.
H2O :
CH2 OH
H+
+
|
H2O CH2
CH2 +
|
OH
CH2
CH2OH
|
CH2OH
(c) Olefins are converted to chlorohydrins and are then hydrolysed with
milk of lime. Ethylene glycol itself is prepared as follows :
CH2
||
CH2
+ HOCl
CH2OH
|
CH2Cl
Ca(OH)2
CH2OH
|
CH2OH
In the above, first step involves addition across the double bond and
the second step a SN2 attack by the OH ion.
The latter two methods are of commercial importance.
2. By substitution reactions :
1,2-dihaloalkanes are hydrolysed with aqueous sodium carbonate.
(a) Ethylene dibromide is heated with moist silver oxide or aqueous
sodium carbonate solution to form ethylene glycol.
165
CH2Br
|
CH2Br
H2O
Na2CO3
CH2OH
|
CH2OH
2 NaBr
CO2
2HNO2
CH2OH
|
CH2OH
2N2
2H2O
4 (H)
8(H)
CH2OH
|
CH2OH
CH2OH
|
CH2OH
2 (H)
2 C2H5OH
CHO
|
CH2OH
glycolic aldehyde
16.4.2 PROPERTIES
Because of the presence of two hydroxyl groups the intermolecular
hydrogen bonding is made much stronger. Hydrogen bond can be formed
between both OH groups resulting in a polymeric structure.
166
H
|
CH2 O -------- H O
|
|
-------- O CH2
CH2 CH2 O -------|
|
H
H
This leads to high viscosity and boiling point (470 K). This is miscible
with water and alcohol in all proportions but immiscible with ether. Water
or alcohol forms stronger H-bonding with glycol, breaking the polymeric
structure. This explains the hygroscopic nature of glycol. It is a colourless
liquid with sweet taste, but toxic in effect.
CHEMICAL PROPERTIES
The molecule of ethylene glycol contains two primary alcoholic groups.
It exhibits the general chemical characteristics of primary alcohols twice
over. However in most of the reactions both these groups are not equally
reactive. One hydroxyl group reacts completely before the other one
participates in the reaction. In general this resembles a primary alcohol in all
chemical reactions.
1. Replacement of acidic hydrogen
The hydrogen atom of the OH group is replaced by electropositive
metals like sodium step by step, with evolution of hydrogen.
CH2OH
|
CH2OH
Na
323 K
CH2ONa
|
CH2OH
Monosodium
glycolate
Na
433 K
CH2ONa
|
CH2ONa
Disodium
glycolate
CH2OH
|
CH2OH
H+
HX
X CH2
+
|
CH2OH
CH2 O
|
CH2OH
H2O
HCl / 433 K
H2O
CH2Cl
|
CH2OH
CH2Cl
|
CH2Cl
HCl / 473 K
H2O
ethylene chlorohydrin
ethylene
dichloride
2HNO3
H2SO4
CH2 O NO2
|
CH2 O NO2
+ 2H2O
(iii) Ethylene glycol reacts with organic acids like acetic acid in presence
of mineral acid, forming glycol mono and diacetate.
CH2OH
|
CH2OH
+ CH3COOH
H+
-H2O
CH2OCOCH3
CH3COOH
|
H+
CH2OH
glycol monoacetate
CH2OCOCH3
|
CH2 OCOCH3
glycol diacetate
Acetyl chloride, acetic anhydride also form the same products with
ethylene glycol.
(iv) Reaction of ethylene glycol with dicarboxylic acid.
Both glycol and dicarboxylic acid being molecules with two functional
groups, react forming condensation polymers. Thus with Terephthalic acid,
ethylene glycol forms the polymer Terylene (also known as dacron or
terene), which is extensively used as a synthetic fibre.
168
COOH
HO[CH2CH2OCO
CH2Cl
|
CH2OH
CH2Cl
|
CH2Cl
CH2Br
|
CH2OH
CH2Br
|
CH2Br
ethylene bromohydrin
ethylene dibromide
CH2I
|
CH2I
CH2
||
CH2
-I2
unstable
3. DEHYDRATION
Ethylene glycol undergoes dehydration under different conditions to
form different products.
(i) When heated alone up to 773 K it forms ethylene oxide or ethylene
epoxide. This is an intra molecular reaction in which a water molecule is
eliminated from the two OH groups.
CH2 OH
|
CH2 OH
H2O
773K
169
CH2
|
CH2
ZnCl2
H2O
H
|
COH
||
CH2
H
|
C=O
|
CH3
HO CH2 CH2
H3PO4
HO CH2 CH2 OH
O
HO CH2 CH2
H2SO4
H OCH2CH2
CH2CH2
H2SO4
O
HO CH2CH2
O
CH2CH2
4. OXIDATION REACTION
Ethylene glycol contains two primary alcohol groups, hence number of
oxidation products are possible. That depends on
(i) The nature of the oxidising agent.
(ii) The quantity of the oxidising agent used.
170
(iii) Whether one or both the primary alcoholic groups are oxidised.
(a) Acidified potassium dichromate or potassium permanganate is very
powerful oxidising agent. Hence they are capable of cleaving the CC bond
forming formic acid.
CH2OH
|
CH2OH
3(O)
HCOOH
+
HCOOH
+ H2O
glycolic
aldehyde
glyoxalic
acid
COOH
|
CH2OH
glycollic acid
171
oxalic
acid
16.4.3 Uses :
(i) As an antifreeze in automobile radiators.
(ii) As a coolant in aeroplane engines.
(iii) As an explosive.
(iv) In the preparation of synthetic fibre, terylene.
(v) As a solvent and preservative.
(vi) In the preparation of numerous compounds like dioxan.
16.5 TRIHYDRIC ALCOHOLS
The compounds containing three hydroxyl groups are known as
Trihydric alcohols. These three hydroxyl groups are attached to three
different carbon atoms for stability of the compound. The most important
compound of the series is glycerol.
3
Saponification Reaction
Glycerol is prepared in a large scale by the hydrolysis of oils or fats
either by using alkali (in soap industry) or by super heated steam (in candle
industry). Hydrolysing with alkali, forms sodium or potassium salt of higher
fatty acids as solids. These are called soaps.
In general hydrolysis of esters using alkali is called Saponification
reaction.
CH2OCOR
|
CHOCOR + 3NaOH
|
CH2OCOR
CH2OH
|
CHOH +
|
CH2OH
3RCOONa
(soap)
CH2OH
|
CHOH
|
CH2OH
H2SO4
Steam
3RCOOH
(solid)
Cl2
773 K
propylene
CH2
||
CH
|
CH2Cl
Na2CO3
773 K/12 atm
allyl chloride
CH2
||
HOCl
CH
|
CH2OH
allyl alcohol
CH2OH
|
CHOH
|
CH2OH
173
CH2OH
|
CHCl
|
CH2OH
glycerol
chlorohydrin
NaOH
+ NaCl
Na
CH2ONa
|
CHOH
|
CH2OH
Na
CH2ONa
|
CHOH
|
CH2ONa
HCl
383K
CH2Cl
|
CHOH
|
CH2OH
glycerol
-chlorohydrin
174
CH2OH
|
CHCl
|
CH2OH
glycerol -chlorohydrin
CH2OH
|
CHCl
|
CH2OH
Excess
HCl
CH2Cl
|
CHOH
|
CH2Cl
CH2Cl
|
CHCl
|
CH2OH
-' dichlorohydrin
,- dichloro
hydrin
HI or
PI3 or I2
CH2I
|
CHI
|
CH2I
CH2
||
CH
|
CH2I
-I2
With excess of the reagent allyl iodide further reacts giving ultimately
isopropyl iodide.
CH2
||
CH
|
CH2I
I Step
HI
CH3
|
CHI
|
CH2I
I2
CH3
|
CH
||
CH2
HI
propylene
III Step
II Step
175
CH3
|
CHI
|
CH3
isopropyl
iodide
conc.H2SO4
CH2ONO2
|
CHONO2
|
CH2ONO2
3H2O
Nitroglycerine
or
Glyceryl trinitrate
Similarly with acetic acid, acetic anhydride (or) acetyl chloride mono,
di and tri acetates are formed depending upon the amount of reagent used.
CH2OCOCH3
|
CHOH
|
CH2OH
Glycerol
Monoacetate
CH2OCOCH3
|
CHOH
|
CH2OCOCH3
Glycerol
Diacetate
CH2OCOCH3
|
CHOCOCH3
|
CH2OCOCH3
Glycerol
Triacetate
6. Dehydration :
When glycerol is heated with potassium bisulphate or conc. sulphuric
acid or phosphorous pentoxide dehydration takes place. Two -elimination
reaction takes place to give acrolein or acrylic aldehyde.
H CH OH
|
H C OH
|
H CH OH
KHSO4
CH2
||
C
||
CHOH
CH2
||
CH
|
CHO
unstable
acrolein
CH2OH
HO C = O
|
|
CHOH +
CO OH
|
CH2OH
CH2 O C = O
|
|
decarboxylation
CHOH
COOH
|
CH2OH
CO2
383K
monooxalate
CH2OCOH
|
CHOH glycerol mono formate
|
CH2OH
This on hydrolysis gives formic acid.
CH2OCOH
|
CHOH
|
CH2OH
CH2OH
|
CHOH
|
CH2OH
HCOOH
formic acid
533K
CH2 O CO
|
|
CH O CO
|
CH2OH
CH2
||
CH + 2CO2
|
CH2OH
unstable
allyl alcohol
[O]
primary alcohol
[O]
CHO
COOH
aldehyde
acid
[O]
[O]
CHOH
> C=O
Secondary alcohol
Ketone
COOH + CO2
etc.
CH2OH
|
CHOH (O)
|
CH2OH
CHO
|
CHOH (O)
|
CH2OH
COOH
|
CHOH (O)
|
CH2OH
CH2OH
|
(O)
CO
prolonged
|
CH2OH
COOH
|
CO
|
COOH
dihydroxy acetone
mesoxalic acid
glyceraldehyde
glyceric acid
(O)
2 CO2 + H2O
(O)
178
COOH
|
+ CO2
COOH
oxalic acid
COOH
|
CHOH
|
COOH
(O)
tartronic acid
16.5.1 Uses :
1. In the manufacture of explosives like TNG.
2. as an antifreeze in automobile radiators.
3. as a sweetening agent in beverages.
4. in moisturising creams and other cosmetics.
5. in copying inks and stamp pad inks.
16.6 AROMATIC ALCOHOL
Benzyl alcohol :
Aromatic compounds containing hydroxyl group in the side chain are
called aromatic alcohols. A typical example is Benzyl alcohol C6H5CH2OH.
It is also called phenyl carbinol or in the IUPAC system phenyl methanol.
CH2OH
The structure is
It can be considered as an arylated aliphatic alcohol. Benzyl alcohol
occurs in nature either in free form or in the form of esters in jasmine oil. It
is isomeric with cresols and anisole.
16.6.1 Methods of preparation :
1. By the hydrolysis of benzyl chloride
Obtained by the chlorination of Toluene followed by hydrolysis with
aqueous NaOH.
C6H5CH3
Toluene
Cl2
HCl
C6H5CH2Cl
NaOH
Benzyl chloride
C6H5CH2OH + NaCl
Benzyl alcohol
3. By Cannizzaro Reaction :
Simple Cannizzaro reaction of benzaldehyde or a crossed Cannizzaro
reaction of a mixture of benzaldehyde and formaldehyde is effected by treating
them with 50% caustic soda solution.
OH
(i) C6H5CHO
C6H5CHO
C6H5CH2OH
+
C6H5COOH
+ H2O
Benzyl alcohol
Benzoic acid
(simple)
(ii) C6H5CHO
HCHO
+ H2O
C6H5CH2OH
+
HCOOH
OH
Benzyl alcohol
Formic acid
(crossed)
C6H5
C=O
ether
H
C
O MgBr
C6H5
CH2 OH
Br
+ Mg
OH
180
H3O+
16.6.2 Properties :
It is a colourless pleasant smelling liquid with b.p. 478 K. It is sparingly
soluble in water, because of the presence of hydrophobic phenyl group (larger
in size when compared to methyl or ethyl group). But it is soluble in organic
solvents like benzene and alcohol.
Chemically it resembles aliphatic primary alcohol.
1. It is not so acidic as to dissolve in sodium hydroxide but reacts with
sodium metal forming sodium benzylate or sodium benzoxide.
2C6H5CH2OH + 2Na
2C6H5CH2ONa
H2
C6H5CH3 + I2
HCl
Acetylchloride
H+
C6H5CH2OCOCH3
H2O
benzyl acetate
C6H5CH2OCOCH3
CO CH3
C6H5CH2 O H + O
C6H5CH2OCOCH3
CO CH3
+ CH3COOH
Acetic anhydride
6. Oxidation :
(i) With mild oxidising agents like copper nitrate or lead nitrate, benzyl
alcohol is converted to benzaldehyde.
C6H5CH2OH
Pb(NO3)2
or Cu(NO3)2
C6H5CHO
H2O
Decomposition of the metallic nitrate provide the source for the above
oxidation.
(ii) In the oxidation with acidified potassium dichromate or alkaline
potassium permanganate, benzaldehyde is first formed which undergoes
further oxidation to benzoic acid.
Na2Cr2O7/H+ or
C6H5CH2OH
C6H5CHO
Na2CO3/KMnO4
Benzaldehyde
C6H5COOH
Benzoic acid
CH2OH
CH2OH
Cl
CH2OH
SO3H
Conc.
Cl2
CH2OH
CH2OH
+
H2SO4
Cl
SO3H
o- and p- chloro
substituted compounds
16.6.3 Uses
(i) Used as a local anaesthetic in intravenus subcutaneous injections.
(ii) as an antiseptic in ointments.
(iii) as esters in perfumery. (Benzyl acetate has fragrance of Jasmine)
(iv) as benzyl benzoate in the treatment of asthma and whooping cough.
(v) in the manufacture of synthetic resins.
16.7 PHENOLS
Phenols : These form a class of compounds in which one or more
hydrogen atom of the benzene nucleus are replaced by hydroxyl group. The
simplest members are phenol [C6H5OH] and cresols [CH3C6H4OH].
Classification and Nomenclature
1. Phenols may be classified as monohydric, dihydric and trihydric
according to the number of hydroxyl groups.
(i) Monohydric phenols :
CH3
OH
CH3
CH3
OH
OH
Hydroxy benzene
(Phenol)
o-hydroxy toluene
(o-cresol)
m-hydroxy toluene
(m-cresol)
OH
p-hydroxy toluene
(p-cresol)
CHO
OH
OH
OH
O2N
COOH
NO2
NH2
o-aminophenol
o-hydroxy
benzaldehyde
NO2
OH
2,4,6-trinitro
phenol
p-hydroxy
benzoic acid
OH
CH3
OH
OH
HO
OH
OH
OH
1,2-dihydroxybenzene
or
ortho dihydroxy
benzene
or
Catechol
OH
OH
OH
OH
OH
HO
OH
OH
1,2,3-trihydroxybenzene
(Pyrogallol)
1,2,4-trihydroxybenzene
(Hydroxy quinol)
1,3,5-trihydroxybenzene
(Phluroglucinol)
Occurence :
Coal tar is the most important source of phenols like phenol, cresol etc.,
from which they are obtained industrially. Some substituted phenols occur
in essential oil of plants like eugenol in clove oil, thymol in mint oil.
184
16.7.1 Preparation
1. From aryl halides : Phenols can be prepared by heating aryl halide,
with caustic soda at high temperature and pressure.
Ar-Cl +
NaOH
C6H5 Cl + NaOH
Chloro benzene
623K
300 atm.
623K
300 atm.
ArOH
NaCl
C6H5OH + NaCl
phenol
SiO2
C6H5OH + HCl
+ NaOH
ArSO3Na + 2NaOH
ArSO3Na + H2O
573 K
Ar ONa + Na2SO3
Sodium phenoxide
ArONa
+ HCl
ArOH + NaCl
Benzene diazonium
chloride
H2O
H+
C6H5OH + HCl + N2
185
OH
NaOH / CaO
COONa
+ Na2CO3
Sodium salicylate
Phenol
AlCl3
CH3
CH3
+ CH3CH=CH2
Cumene
CH3
|
H3C COOH
OH
H+
CH3
+ O=C
H2O
CH3
Phenol
186
Acetone
16.7.2 Properties
1. Pure phenols are colourless liquids or crystalline solids. They turn
pink or red on exposure to air and light due to oxidation.
2. Lower phenols have characteristic Carbolic acid - odour.
3. They are insoluble or sparingly soluble in water but dissolve readily in
alcohol and ether. Relatively high boiling point of phenols and solubility
in alcohols can be explained by intermolecular hydrogen bonding.
Insolubility in water is explained by the presence of hydrophobic phenyl
group.
16.7.3 General chemical properties
Phenols exhibit reactions of both the hydroxyl group and aromatic ring.
They differ from alcohols in having weakly acid character and in not
undergoing elimination and substitution reactions.
Reactions of hydroxyl group
In some reactions phenols resemble alcohols. In many others they differ
from alcohols.
Reactions different from alcohols
1. They form water soluble coloured complexes with neutral ferric
chloride. The colour of the complex vary from violet, red, blue or
green. Since different phenols give different colours.
Phenol itself gives violet colour. It is a characteristic test for phenol.
2. Acidic character
Phenols are weakly acidic. These are stronger acids than alcohols but
weaker than all mineral acids, carboxylic acids and even carbonic acid.
Hence phenols dissolve in sodium hydroxide (a strong base) but not in
sodium bicarbonate (weaker base). This property is used in the
separation of phenols from carboxylic acids.
C6H5OH + NaOH
C6H5ONa + H2O
Sodium phenoxide
2C6H5OH +
2C6H5ONa + H2
2Na
OH
H2O
H3O+
Phenol
Phenolate ion
()
()
()
RCH2OH
OH
>
>
NO2
OH
OH
Cl
>
CHO
OH
>
NO2
188
CH3
:OH
etc.
N+
N
O()
()O
O()
etc.
N+
O
N+
O()
()O
O()
Phenolate ion has no +ve charge on oxygen and hence is more stabilised
by resonance than phenol itself.
Consequence of this Resonance
1. Phenols are stronger acid than alcohols (because the RO-alkoxide
ions are not stabilised by resonance).
2. The electron density is increased in the benzene ring and hence the
benzene ring is activated towards electrophilic substitution reaction.
3. Ortho and para positions are more electron dense, and the electrophilic
substitution takes place at ortho and para positions.
4. Oxygen is strongly bound to the nucleus hence it is not easily removed.
The acid strength of phenols depend on the nature of the substituent
present in the benzene ring. Electron withdrawng groups like -Nitro, cyano
groups increase the acid strength. Electron donating substituents like NH2,
CH3- groups decrease the acid strength. (e.g.,) strength of phenol varies in
the order.
189
OH
OH
>
OH
>
CN
NO2
OH
>
OH
>
CHO
CH3
ArH
Zn
C6H5OH + Zn
ZnO
C6H6 +
ZnO
C6H5OH +
CH3COOH
C6H5COOCH3 + H2O
Phenyl acetate
Acid chlorides and acid anhydrides react with phenols giving esters more
easily, especially in presence of a base.
C6H5 OH + CH3 COCl
OH
C6H5 OH + CH3COOCOCH3
OH
C6H5OCOCH3 + HCl
C6H5OCOCH3 + CH3COOH
190
C6H5OH + C6H5COCl
NaOH
C6H5OCOC6H5 + HCl
Phenyl benzoate
2) Etherification
Phenols react with alkyl halides or alkyl sulphates in presence of alkali
to form phenolic ethers. Aryl halides do not react with phenols. This alkylation
of phenol is a nucleophilic substitution reaction. This reaction is known as
Williamsons synthesis.
NaOH
ArOH
ArO()
ArO() + R X
C6H5OH + (CH3)2 SO4
Dimethyl sulphate
C6H5OH + C2H5Br
+ X
ArOR
NaOH
OH
Na+
C6H5OCH3 + CH3OSO2OH
Anisole
C6H5Cl
POCl3
HCl
Cl PCl3 Cl
The yield of chloro benzene is very small and the main product is triphenyl
phosphate (C6H5O)3PO. (Compare this reaction with alcohol)
191
OH
+ CH2N2
C6H5OCH3
diazomethane
N2
Anisole
ArOH
C6H5OH
NH3
+
ArNH2
ZnCl2/473 K
NH3
C6H5NH2
Phenol
H2O
+
H2O
Aniline
OH
3 Br2
Br
Br
3 HBr
H2O
Br
2, 4, 6-tribromo phenol.
OH
OH
Br
2 Br2
+ 2HBr
CCl4
Br
ortho bromo phenol
2. NITRATION
Reaction with nitrating mixture - con. H2SO4 acid and con. Nitric acid
mixture-gives picric acid.
OH
OH
O2N
298 K
NO2
3 H2O
H2SO4/HNO3
NO2
2, 4, 6-trinitro phenol (Picric acid)
With dilute nitric acid, a mixture of ortho and para nitro phenols are
formed.
OH
OH
HNO3
OH
NO2
+
NO2
193
SULPHONATION
Reaction with con. H2SO4. It forms a mixture of ortho and para phenol
sulphonic acid.
OH
OH
OH
SO3H
293 K
Conc. H2SO4
SO3H
Ortho hydroxy benzene
Sulphonic acid
NITROSATION
It reacts with nitrous acid (a mixture of sodium nitrite and sulphuric
acid) to give p-nitrosophenol.
OH
OH
200 K
HNO2
NO
para nitroso phenol
OH
OH
N=N
273 K
(Benzene diazonium chloride)
OH
OH
CO2
400 K
4 - 7 atm
HCl
COONa
OH
+ NaCl
COOH
Riemer-Tiemann reaction
This reaction is an example of formylation reaction. When phenol is
refluxed with chloroform and sodium hydroxide, a formyl group CHO is
introduced at the ortho or para position to OH group.
OH
OH
CHCl3
NaOH
OH
+
CHO
OHC
Ortho
Para
(Hydroxy benzaldehyde)
OH
CCl4
OH
NaOH
COOH
HOOC
Ortho
Para
(Hydroxy benzoic acid)
Phthalein fusion
Phenols are heated with phthalic anhydride and con. H2SO4 to give
Phenolphthalein. This can be tested by the formation of pink colour when it
is treated with sodium hydroxide.
195
O
C
OH
C=O
H
OH
C
OH
OH
Phenolphthalein
Oxidations
Phenol undergoes oxidation to quinone on treatment with chromyl
chloride (CrO2Cl2).
OH + 2 ( O)
CrO2Cl2
Catalytic hydrogenation
Phenol on hydrogenation in presence of nickel forms cyclohexanol.
OH
OH
Ni
+ 3 H2
443 K
(Cyclohexanol)
Condensation :
Phenol, when treated with formaldehyde and sodium hydroxide,
undergoes condensation reaction.
HO
NaOH
+ HCHO
HO
CH2OH
p-hydroxy phenyl methanol
OH
CH2
CH2
|
CH2-------
CH2
|
Bakelite
16.7.4 Uses
Phenol is of much industrial importance. It is used in the manufacture of
dyes, drugs, plastics, explosives, pesticides etc. Phenol is an antiseptic and
germicide. It is used in some soaps and lotions.
SELF EVALUATION
(A) Choose the correct answer :
1. Which has the highest boiling point ?
(a) CH3CH3
(b) CH3OH
(c) C2H5OH (d) C3H8
2. Which is soluble in H2O ?
(a) Phenol
(b) Alkanes
(c) Alcohols (d) Alkenes
3. Order of reactivity of alcohol towards sodium metal is
(a) primary < secondary > tertiary
(b) primary > secondary > tertiary
(c) primary < secondary < tertiary
(d) primary > secondary < tertiary
4. The boiling point of ethyl alcohol should be less than that of
(a) propane
(b) formic acid
(c) dimethyl ether
(d) None of the above
5. Ethyl alcohol cannot be used as a solvent for CH3MgI because
(a) CH3MgI reacts with alcohol giving methane
(b) The reaction between them is explosive in nature
(c) CH3MgI is converted to C2H5MgI
(d) Alcohol is immicible with CH3MgI
197
(a)
(b)
N
+
N
()O
O()
O
O
(c)
(d)
N
+
O
O()
198
N
+
O
(b) (CH3)2CHOH
(d) CH3CH2OH
(b) benzene
(d) toluene
(b) propanol
(c) glycerol
(d) glycol
(b) 2
(c) 3
(d) 0
NH3
Al2O3
360oC
con.H2SO4
excess
202
Ag+
NaOH
CH3
Ans.
OH
OH
COOH
CHO
A=
B=
CH3
CH3
403 K
6 atm
dil. HCl
Ans.
OH
OH
COONa
C=
COOH
D=
A and B
[O]
[O]
prolonged
A = CH3 C CH3
||
O
[O]
203
CH3 COOH
B
34. What are monohydric alcohols ? How are they classified ? Give any
three methods of preparing ethyl alcohol.
35. How will you distinguish the primary, secondary and tertiary alcohols by
Victor Meyers method ?
36. Write equation for the following conversions.
(a) Ethyl alcohol
ethylene
diethyl ether
ethyl amine
204
Problem.
Ethylene glycol
Ans.
CH3CH2OH
Al2O3
CH2 = CH2
620K
cold alkaline
KMnO4
(Baeyers reagent)
CH2 CH2
|
|
OH OH
2. Give the IUPAC names of
(i) CH3CH(OH)CH2OH
(ii) HOCH2CH2OH
(iii) CH3CHCOOH
|
OH
Ans.
205
dil.H2SO4
[O]
SOCl2
HgSO4
Ans.
A = CH3CHO
B = CH3COOH
C = CH3COCl
(ii) C2H5OH
PCl5
KCN
H2O/H+
sodalime
Ans.
A = C2H5Cl
B = C2H5CN
C = C2H5COOH
D = C2H6
+ LiAlH4
4H2
206
+ LiAl(OCH3)4
6. When tertiary butyl alcohol and 1-butanol are separately treated with a
few drops of KMnO4, in one case only the purple colour disappears and
a brown precipitate is formed. Which of the two alcohols gives the above
reaction and what is that brown precipitate.
Ans. 1-butanol, being primary alcohol gets oxidised by dilute KMnO4.
The brown precipitate is due to the formation of manganese dioxide.
2KMnO4 + H2O
3KOH
manganese dioxide
(brown precipitate)
CH3CH2CH2CH2 OH +
1-butanol
+ 2MnO2 + 3 (O)
2(O)
room temp.
Ca(OH)2
CH3COOH
(CH3COO)2Ca
calcium acetate
CH3COCH3
acetone
CH3MgBr
CH3
|
CH3 C OH
|
CH3
Tert. butyl alcohol
NaOH
CH3CHOHCH2CHO
(D)
aldol
heat
H2O
CH3 CH = CH CHO
2-butenal (E)
H2
LiAlH4
(B)
butyl alcohol
(C)
Ans.
CH2OH
2. Why sodium metal cannot be used to dry alcohols but it can be used to
dry ethers ?
Ans. Alcohols are acidic enough to react with sodium but ethers are
inert.
208
CH3CH2CH2CH2OOCCH3
PRACTICE QUESTIONS.
1. Give the IUPAC names of each of the following and classify them as 1o,
2o and 3o.
(a) CH3(CH2)3CHOHCH(CH3)2
(b) (CH3)3CCH2OH
(c) (CH3)2 C OH
|
C6H5
(f) PhCH2OH
(b) (CH3)2C(OH)CH2CH2CH3
209
(d)
C6H5
|
CH3CH2 C CH3
|
C6H5
(b) (CH3)3CBr
(c) CH3CH2Li
13. Which member of the following pairs would you expect to be more water
soluble ?
(a) CH3 CH2 OH or CH3 CH2 OCH3
(b) CH3 COOH or HCOOCH3
14. Which member of the following pairs would you expect to have higher
boiling point ?
CH3 O CH2 CH2 O CH3 or CH2 OH CH2 CH2 CH2 OH
Cl CH2 CH2 OH or CH2 OH CH2 OH
210
KHSO4
KOH (aq)
product
acrolein
(ii) glycol
dioxan
formic acid
C2H4
(ii) glycerol
O2/Ag
H2SO4/H2O
523 K
473K
HNO3
HNO3
(O)
(O)
Na2CO3/H2O
HOCl
Formaldehyde
(ii) glycerol
TNG
(iii) glycerol
Glycerol Triacetate
211
NaOH
Phenols
OH , MeO
OH , O2N
OH , CH3
OH
212
17. ETHERS
LEARNING OBJECTIVES
@ Ethers - structure, classification, isomerism and nomenclature.
@ General methods of preparation - properties - physical and chemical
properties - uses.
@ Aromatic ethers - nomenclature.
@ The methods of preparation of anisole - its physical and chemical
properties - uses.
17.1 ETHERS
These are compounds of the type ROR, where oxygen atom is linked
to both sides by either saturated, unsaturated or aromatic carbon. Their
general formula is ROR'.
CLASSIFICATION
Simple ethers :
If the two alkyl groups attached to the oxygen atom are the same
(R = R') then it is called a simple or symmetrical ether.
CH3 O CH3
dimethyl ether
C2H5 O C2H5
diethyl ether
Mixed ethers :
If the two alkyl groups are different then they are called as mixed or
unsymmetrical ethers.
(e.g.,)
CH3 O C2H5
ethyl methyl ether
If one or two aryl groups are attached to the oxygen atom then they are
called as aromatic ethers. For example
C6H5OCH3
C6H5OC6H5
anisole
diphenyl ether
Nomenclature :
Common system - Ethers are named by prefixing the names of alkyl
groups attached to the oxygen atom before the word ether. Thus
CH3OCH3 is dimethyl ether CH3OC2H5 is ethyl methyl ether.
215
IUPAC name
Common name
CH3 O CH3
CH3 O C2H5
CH3 O CH2CH2 CH3
CH3 O CH CH3
|
CH3
Methoxy methane
Methoxy ethane
1-methoxy propane
2-methoxy propane
Dimethyl ether
Ethyl methyl ether
methyl n-propyl ether
methyl iso propyl ether
Isomerism :
Ethers are functional isomers of alcohols as both have the same general
formula CnH2n+2O.
The C2H6O stands for both CH3CH2OH and CH3 O CH3.
Functional Isomerism
Molecular formula
C3H8O
Ethers
Alcohols
CH3OCH2CH3
CH3CH2CH2OH
n-propyl alcohol
CH3 CH CH3
|
OH
isopropyl alcohol
C4H10O
CH3CH2OCH2CH3
CH3CH2CH2CH2OH
diethyl ether
n-butyl alcohol
CH3OCH2CH2CH3
CH3CHCH2OH
|
CH3
methyl-n-propyl ether
isobutyl alcohol
CH3OCHCH3
|
CH3
CH3CH2CHCH3
|
OH
sec.butyl alcohol
CH3
|
CH3COH
|
CH3
tert. butyl alcohol
216
Metamerism :
It is a special isomerism in which molecules with same formula, same
functional group, differing only in the nature of the alkyl group attached to
oxygen.
CH3 O CH2CH2CH3
CH3CH2OCH2CH3
methyl-n-propyl ether
diethyl ether
CH3
|
CH3OCHCH3
methyl isopropyl ether
H2SO4
C2H5 O H + H O C2H5
413K
con. H2SO4
R O R + H2O
C2H5 O C2H5
C2H5
|
O+ H
|
H
C2H5 O C2H5
+ H+ + H2O
250oC
Al2O3
C2H5 O C2H5
+ H2O
2. Williamsons synthesis
This is the most important method. It consists of heating alkyl halides
with sodium or potassium alkoxide.
217
RX
+ NaOR'
ROR' + NaX
C2H5Br
+ NaOC2H5
C2H5 O C2H5
CH3Br
+ NaOC2H5
CH3 O C2H5
methyl bromide
sodium ethoxide
+ NaBr
+ NaBr
R O + R' Br
R O R'
+ Br
This method is suitable to prepare all kinds of ethers - simple and mixed
ethers.
3. From alkyl halides
By heating alkyl halides with dry silver oxide, ethers may be prepared.
RX
+ Ag2O +
XR
ROR
+ 2AgX
Mixed ethers can be prepared by taking different alkyl halide with dry
silver oxide.
CH3I
+ Ag2O + I C2H5
methyl iodide
R O Ag
ethyl iodide
CH3OCH2CH3 + Mg
218
Cl
17.2.1 Properties
(i) Lower members are gases, higher members are pleasant smelling volatile
liquids.
(ii) insoluble in water, soluble in organic solvents. These can be explained
on the basis of the absence of hydrogen bonding.
(iii) Ethers are lighter than water. Lower members are inflammable.
(iv) Lower ethers act as anaesthetics.
Chemical Properties :
These are chemically almost inert and do not react with acids, alkalies,
electro positive metals like sodium.
(i) Reaction of the alkyl radicals (substitution reactions)
(ii) Ether oxygen-capable of donating a pair of non bonding electrons.
(iii) The CO bond which is not as stable as CC bond, is cleaved.
Reaction of alkyl groups :
1. Halogenation
Ethers undergo substitution at the alkyl group when treated with chlorine
or bromine in absence of sunlight. Usually -hydrogen is substituted more
readily.
R O CH2 CH3
C2H5 O C2H5
Cl2
Cl
|
R O CH CH3
-chloro ether
Cl2
dark
Cl2
light
C2Cl5 O C2Cl5
..
RO
.. R or
ROR
:O
.. :
C2H5 O C2H5
(C2H5)2O2
diethyl peroxide
..
ROR+HX
..
C2H5 O C2H5 + HCl
C2H5 O C2H5
|
H
diethyl ether
220
Cl
H
|
(R O R) HSO4
R O R + H2SO4
H
|
(C2H5 O C2H5) HSO4
O BF3
R
(Boron trifluoride etherate)
C2H5
O : BF3
C2H5
OR2
Mg
R2O
X
CH3
2 C2H5OC2H5 + CH3MgI
diethyl ether
O(C2H5)2
Mg
methyl magnesium
iodide
221
O(C2H5)2 I
ROR + HOH
2R OH
H2SO4
C2H5 O C2H5 + H O H
2C2H5OH
R2 OH
OH2
R O+ R'
R OH + R' OH + H+
|
H
(ii) Reaction with HX
On treating with HBr or HI ether gets cleaved to form alcohol and alkyl
halide.
H
..
|
R O R + HI
R O+ R
RI + HOR
I
Halogen prefers to attack the carbon atom of the smaller alkyl group.
C2H5 O CH3
HI
C2H5OH + CH3I
(iii) With excess hot concentrated hydroidic acid, alkyl iodides are formed.
CH3 O C2H5
2HI
CH3I
+ C2H5I
+ H2O
Cl PCl3 Cl
C2H5OC2H5+ PCl5
2C2H5Cl + POCl3
Name in common
system
Name in IUPAC
system
C6H5OCH3
methoxy benzene
C6H5OC2H5
ethoxy benzene
C6H5 O C6H5
diphenyl ether
phenoxy benzene
223
17.3.1 Preparation
1. Williamsons synthesis :
By heating sodium phenoxide with methyl iodide. This reaction
follows SN2 pathway. The nucleophile is C6H5O (phenoxide ion) and the
substrate is methyl iodide.
C6H5O Na+ + CH3 I
C6H5O + C2H5I
C6H5 O C2H5 + I
(phenetole)
3. Manufacture of ether :
Large scale methylation of phenol is carried out using dimethyl
sulphate in presence of sodium hydroxide.
C6H5OH
(CH3)2SO4
NaOH
C6H5OCH3
CH3.HSO4
C6H5OCH3 + OSO2OCH3
Chemical Properties
1. It forms oxonium compounds with Lewis acids
AlCl
3
..
C6H5OCH3
AlCl3
|
C6H5 O CH3
+
BF
..
C6H5OCH3
BF3
|
C6H5 O CH3
+
I + CH3 O+ C6H5
|
H
I CH3 + HOC6H5
phenol
(protonated ether
OCH3
NO2
OCH3
con. HNO3
con.H2SO4
NO2
225
OCH3
Br
Br2
OCH3
Br
Aliphatic ethers
(Diethyl ether)
Volatile liquid
2. Used in perfumery.
Used as anaesthetic.
Used as a solvent.
5. On heating with HI
forms phenol and CH3I only.
226
SELF EVALUATION
(A) Choose the correct answer :
1. The isomerism exhibited by C2H5OC2H5 and CH3 O CH CH3 is
|
CH3
(a) Functional
(b) metamerism
(c) position
(d) chain
2. Which one of the following is simple ether ?
(a) CH3 O C2H5
(b) C2H5 O CH3
(c) C2H5 O C2H5
(d) C3H7 O C2H5
3. Diethyl ether can be decomposed with
(a) HI
(b) KMnO4
(c) NaOH (d) H2O
4. Oxygen atom of ether is
(a) very active (b) Replacable
(c) oxidising
(d) Comparatively inert
5. According to Lewis concept of acids and bases, ethers are
(a) Neutral
(b) Acidic
(c) Basic
(d) Amphoteric
6. Intermolecular hydrogen bonds are not present in
(a) CH3COOH (b) C2H5OC2H5
(c) CH3CH2OH (d) C2H5NH2
7. When ethyl Iodide is treated with dry silver oxide it forms
(a) Ethyl alcohol
(b) diethylether
(c) silver ethoxide
(d) ethylmethyl ether
8. Williamson's synthesis is an example of
(a) nucleophilic addition
(b) electrophilic addition
(c) electrophilic substitution
(d) Nucleophilic substitution reaction
9. When ether is exposed to air for sometime an explosive substance
produced is
(a) peroxide
(b) oxide
(c) TNT
(d) superoxide
10. Ether is formed when alkylhalide is treated with sodium alkoxide. This
method is known as
(a) Hoffmann reaction
(b) Williamson's synthesis
(c) Wurtz synthesis
(d) Kolbe's reaction
227
250oC
Al2O3
229
Reduction
(Oxidation state
2 in alcohol)
O
||
H C OH
Oxidation
C
||
O
(Oxidation state
+2 in carboxylic acid)
(Oxidation state
is zero in aldehyde)
Ketones
C=O
C=O
Example
CH3
CH3
C=O
H
C=O
H3C
(Acetaldehyde)
(Acetone)
231
R
C=O
R'
CH3CHO
Acetic acid
Acetaldehyde
C4H9CHO
Pentanalehyde
In the IUPAC system, the prefix indicating the length of the carbon
chain is followed by the suffix al in place of e.
CH3CH2CH2CHO
Butane + al = butanal
Since the aldehyde group is always present in the end it is not shown by
any number.
Common name for ketones is arrived at by adding the suffix ketone
to the name of alkyl groups present
CH3COCH2CH3
Ethyl methyl ketone
232
3-pentanone
Formula
Common name
IUPAC name
HCHO
Formaldehyde
Methanal
CH3CHO
Acetaldehyde
Ethanal
Isobutyraldehyde
2-methyl propanal
CH3
|
CH3 CHCHO
CH2 = CHCHO
CH3 CH = CH CHO
Crotonaldehyde
2-butenal
C6H5CHO
Benzaldehyde
Phenyl methanal
C6H5CH = CHCHO
Cinnamaldehyde
3-phenyl-2-propenal
3-hydroxy butanal
233
KETONES
Formula
Common name
IUPAC name
CH3COCH3
Acetone
Propanone
CH3COCH2CH3
2-butanone
CH3CH2COCH2CH3
Diethyl ketone
3-pentanone
CH3 COCH2CH2CH3
methyl, n-propyl ketone
O
||
CH3 CCH2 CH = CH2 Allyl methyl ketone
2-pentanone
4-pentene-2-one
ISOMERISM
Aldehydes exhibit (i) chain isomerism and (ii) functional isomerism.
Chain Isomerism arises due to changes in carbon chain.
(i) CH3 CH2 CH2 CHO
and
butanal
CH3
|
CH3 CH CHO
2-methyl propanal
CH3
|
H3C C CHO
|
CH3
Pentanal
2,2-dimethyl propanal
Functional isomerism :
2-propen-1-ol
O
||
CH3 CH2 CH2 C CH3
O
||
CH3 CH C CH3
|
CH3 3-methyl-2-butanone
2-pentanone
234
Positional Isomerism :
The carbonyl group may occupy different positions in the carbon chain
to give Positional Isomers.
O
||
CH3 CH2 C CH2 CH3
O
||
CH3 CH2 CH2 C CH3
3-pentanone
2-pentanone
CH3 CH O
|
| +
H
H
(O)
CH3 CH = O + H2O
acetaldehyde
primary alcohol
ethyl alcohol
(CH3)2 C O
| |
H H
K2Cr2O7/H+
(CH3)2 C = O + H2O
(O)
acetone
(CH3)2 CHOH
O2/Ag
520K
O2/Ag
CH3CHO
acetaldehyde
(CH3)2 CO
520K
acetone
235
573 K
RCH = O + H2
Cu
aldehyde
1o alcohol
573K
CH3 CHOH
|
H
CH3 CHO + H2
Cu
acetaldehyde
Ethyl alcohol
R2 C O
|
|
H
H
573 K
Cu
R2C = O + H2
ketone
2o alcohol
CH3
CH3
C O
|
|
H
H
573K
Cu
Isopropyl alcohol
CH3
C = O + H2
CH3
acetone
OCOH
Ca + Ca
CH3COO
OCOH
Calcium acetate
Calcium formate
236
CH3
|
2 HC=O + 2CaCO3
Acetaldehyde
CH3
|
+ CaCO3
CH3 C = O
Ca
CH3COO
calcium acetate
acetone
Pd
HH
Pd
BaSO4
acetyl chloride
BaSO4
RC=O
|
H
CH3 C = O
|
H
HCl
+ HCl
acetaldehyde
2R C = O
|
R'
237
CdCl2
Cl
+ 2 NaOH
Cl
CH3CH
OH H O
2
CH3CHO
OH
ethylidene chloride
acetaldehyde
Cl
C
CH3
+ 2 NaOH
Cl
HOH
CH3
OH
C
CH3
CH3
H2O
C=O
OH
2,2-dichloro propane
CH3
acetone
5. By ozonolysis :
RCH CHR'
O
Zn/HCl
(Ozonide)
RCH + R' CH
||
|| + H2O
O
O
(Aldehyde)
O
R2C = CR'2 + O3
R2C
CR'2
O
O
(ozonide)
238
Zn/HCl
||
||
(ketone)
RCHO + R'CHO
HIO4
Aldehydes
CH3 CHOH
...................
|
CH3 CHOH
HIO4
2CH3CHO
acetaldehyde
butane-2,3-diol
R2 C OH
...................
|
R'2C OH
HIO4
R2CO + R'2CO
(ketone)
(CH3)2 C OH
...................
|
(CH3)2 C OH
HIO4
2CH3 COCH3
acetone
butane-2,3-dimethyl-2,3-diol
7. Hydration of Alkynes
By the hydration of alkynes in 42% sulphuric acid containing HgSO4 as
a catalyst. Acetaldehyde is obtained when acetylene is used. Acetone is
obtained using propyne.
(Acetylene) CH CH
H2
(Propyne)
H+
Hg2+
CH3CHO (acetaldehyde)
CH3C CH
H+
O H2
Hg2+
239
CH3COCH3 (acetone)
8. Stephens reaction :
Aldehyde can be prepared by Stephens reaction, by the reduction of
alkyl cyanide dissolved in ether with Stannous chloride and hydrochloric
acid.
CH3 C N
SnCl2
CH3 CH = NH.HCl
HCl
Iminimum hydro chloride
HH
methyl cyanide
O H2
CH3 CH = NH.HCl
Hydrolysis
CH3CHO + NH4Cl
acetaldehyde
18.3.1 PROPERTIES
Physical properties
C=O
Nu
C O
|
Nu
240
Both charged and uncharged nucleophiles can attack the carbonyl carbon
to form addition products. This is the most common reaction for aldehydes
and ketones.
2. Another kind of reaction of aldehydes and ketones which contain atleast
one -hydrogen atom.
H CH2
CH2
C=O
C=O
BH
Aldehydes are more reactive than ketones for both steric and electronic
reasons.
The presence of alkyl group increases the crowding near carbonyl group
and also increases the electron density at the carbonyl carbon by Inductive
effect. (+I effect)
H
R
C=O
R
C=O
Most reactive
C=O
R
less
least
CH3CHO
+ 3Cl2
CCl3 CHO
(Acetaldehyde)
CH3COCH3
+ 3HCl
(Trichloro acetaldehyde)
+ 3Cl2
(Acetone)
(Trichloro acetone)
CH3
C=O
CH2
H+
Cl Cl
C=O
Cl
|
CH2
R
(carbanion)
(ketone)
(b) Addition reactions.
C = O + Cl
R
(-chloroketone)
H X
C OH
|
X
The negative part of the addendum adds to the carbon and the positive
part to the oxygen.
In the addition of sodium bisulphite to give bisulphite compound
OSO2Na anion is the nucleophile.
OH
C = O + H OSOONa
C
OSO2Na
CH3CHO
HOSO2Na
CH3
OH
C
OSO2Na
CH3
C = O + HOSO2Na
CH3
H3C
OH
C
H3C
OSO2Na
acetone bisulphite
242
Aldol Condensation :
OH
CH2 C = O
|
H
+ H2O
Step 2 :
H
|
CH3 C O
|
CH2 CHO
CH2 CHO
alkoxide ion
Step 3 :
H
|
CH3 C OH + OH
|
CH2CHO
H OH
Aldol
CH2 C = O
|
CH3
OH
Acetone
Carbanion
243
+ H2O
CH3 C O
CH3 C = O
|
CH3
CH2 COCH3
CH3
CH2COCH3
(Nucleophilic attack)
CH3 C O
CH3
H2O
Protonation
CH3
CH2COCH3
OH
C
CH2COCH3
CH3
When an aldehyde and a ketone react in the same way it is called crossed
aldol condensation.
CH3 C = O
|
H
OH
CH2 C = O
|
H
H3C
+ H2O
CH3
C = O
C O
CH3
CH2CHO
CH3
H2O
C
H3C
H3C
CH2CHO
OH
C
H3C
CH2CHO
CH3 CH = CH CHO
H2O
Crotonaldehyde
(v) This reaction is characteristic of carbonyl compounds having hydrogen atom. If there is no -hydrogen atom in the carbonyl compound,
aldol condensation does not take place.
HCHO,
C6H5CHO,
Formaldehyde, Benzaldehyde
C6H5COC6H5.
Benzophenone
R
C=O
OH
C
HCN
R'
R'
CN
Cyano hydrin
OH
H2O
CN
Nucleophile
Step 2 : The cyanide ion attacks the carbonyl carbon to form an anion.
O
C = O
CN
C
CN
245
Step 3 : The proton from the solvent combines with the anion to give
cyanohydrin.
O
OH
+ H+
CN
CN
Cyano hydrin
H+/H2O
CH3 CH COOH
|
OH
Acetaldehyde cyanohydrin
Lactic acid
R
C = O + R MgX
H3O+
OMgX
+ Mg
OH
OH
(i)
H C = O + CH3 MgI
|
H
CH3
|
HO
H C OMgI 2
|
H
formaldehyde
CH3
|
H C OH
|
H
primary alcohol
(ethyl alcohol)
246
CH3
(ii)
|
CH3 C OMgI
|
H
CH3 C = O + CH3MgI
|
H
H2O
acetaldehyde
CH3
|
CH3 C OH
|
H
Secondary alcohol
Iso propyl alcohol
CH3
|
CH3 C OMgI
|
CH3
(iii)
CH3 C = O + CH3 MgI
|
CH3
acetone
H2O
CH3
|
CH3 C OH
|
CH3
tertiary butyl alcohol
Addition of ammonia
CH3
C=
OH
O + HNH2
H2O
CH3CH = NH
NH2
Aldimine
Acetaldehyde ammonia
4NH3
(CH2)6 N4
+ 6H2O
H2C
CH2
CH2
CH2
N
CH2
247
H2 N H
+
= O
O = CHC6H5
C6H5CH= N
H2 N H
CHC6H5
C6H5CH= N
Hydro benzamide
+ HNH2
CH3
|
CH3 C OH
|
NH2
acetone ammonia
CH3
|
CH3 C OH + CH3 C CH3
|
||
NH2
O
CH3
|
high temp
CH3 C CH2 C CH3
H2O
|
||
NH2
O
diacetone amine
CH3 CH = O +
HNH
.. OH
CH3 CH
NHOH
acetaldehyde
hydroxylamine
H2O
CH3CH = NOH
acetaldehyde oxime
248
(b)
OH
C6H5CHO + HNHOH
..
C6H5CH = NOH
NHOH
benzaldehyde
CH3
H2O
C6H5 CH
CH3
OH
C = O + HNHOH
..
CH3
Benzaldoxime
H3C
H2O
C
CH3
NHOH
C = NOH
H3C
Acetone oxime
CH3 OH
C = O + NHNH2
CH3
H2O
C
H
NHNH2
acetaldehyde
CH3
H
acetaldehyde hydrazone
CH3
OH
C = O + H NHNH2
CH3
C = NNH2
CH3
H2O
C
CH3
C = NNH2
NHNH2
CH3
Acetone
Acetone hydrazone
C6H5
C = O + HNHNHC6H5
(a)
OH
C
H2O
C6H5
C = NNHC6H5
NHNHC6H5 H
benzaldehyde
CH3
CH3
C = O + HNHNHC6H5
(b)
CH3
C
CH3
acetone
249
OH
H2O
CH3
NHNHC6H5
benzaldehyde
phenyl hydrazone
C = NNHC6H5
CH3
acetone phenyl
hydrazone
CH3
CH3
C = O + HNHNHCONH2
OH
C
acetaldehyde
NHNHCONH2
H2O
CH3
C = NNHCONH2
H
acetaldehyde semicarbazone
(b)
C6H5
C6H5
C = O + HNHNHCONH2
OH
C
NHNHCONH2
Benzaldehyde
H2O
C6H5
C = NNHCONH2
H
benzaledehyde semicarbazone
The products of reduction depends upon the reagents used and the
conditions of reactions. Hence a variety of reagents are used for reduction.
(i) Catalytic reduction : Aldehydes are reduced to primary alcohols by
hydrogen gas in presence of platinum metal as a catalyst.
R
C=O
H2/Pt
CHOH
H
250
Pt
C=O
R H H
CH3
Pt
H2
C=O
CH3 HH
R2CHOH
CH3
CHOH
CH3
Isopropyl alcohol
NaBH4
CH3
C O
H+
CH3
OH
C
Acetaldehyde
Ethanol
Zn/Hg
HCl
CH3
CH2
+ H2O
CH3
(Propane)
251
In the absence of mercury, hydrogen gas will be evolved and the reduction
is incomplete. This reduction is called Clemmenson reduction.
(ii) Reduction under strongly basic condition :
Wolff-Kishner Reduction
Aldehydes and ketones are reduced to hydrocarbons by heating with
hydrazine and sodium ethoxide.
CH3
C=O
H
CH3
N2H4
C2H5ONa
CH2 + N2 + H2O
H
C=O
|
Aldehydes have
bond which is responsible for their reducing
H
properties. Ketones do not have such a structure and are not reducing agents.
RCHO
Aldehyde
RCOOH
Acid
CH3COOH
(3c)
(2c)
252
Popotts Rule :
b cleavage
HCOOH
CH3CH2CH2COOH
CO2 + H2O
n-butyric acid
CH3COOH
acetic acid
minor products
CH3CH2COOH
propionic acid
major produts
Because aldehydes are easily oxidised, they are reducing agents. They
reduce ammonical silver nitrate (Tollens reagent) to metallic silver and
Fehlings solution (copper sulphate, sodium potassium tartrate) to red cuprous
oxide.
CH3CHO + 2Ag+ + 3OH
Acetaldehyde
(silver mirror)
(blue)
cupric ion
(red precipitate)
cuprous ion
253
H
|
C=O
|
H
H
|
CO
|
H
n
3CH3CHO
CH3
|
CH
con.H2SO4
CH3CH
CHCH3
O
Paraldehyde
Questions.
1. Which among the following reduces (a) Tollens reagent only
(b) Tollens and Fehling solution (c) None
C6H5CHO, CH3CHO, CH3COCH3, HCHO
Answers. (a) C6H5CHO
(c) CH3COCH3
OH
CH3CHOH CH2CHO
H2O
CH3CH = CHCHO
Formula
Common Name
IUPAC name
C6H5CHO
Benzaldehyde
Phenyl methanal
C6H5CH2CHO
Phenyl acetaldehyde
Phenyl ethanal
Salicylaldehyde
2-hydroxy
benzaldehyde
Cinnamaldehyde
3-phenyl prop-2-enal
CHO
OH
C6H5CH = CHCHO
CHO
Benzaldehyde :
18.5 PREPARATION
1. Toluene is oxidised by chromium trioxide and acetic anhydride or
chromyl chloride or air in presence of V2O5 at 773 K.
C6H5CH3
Toluene
(O)
C6H5CHO
air/V2O5 Benzaldehyde
773K
255
+ H2O
Pb(NO3)2
HNO3
C6H5CH2Cl
Benzyl chloride
HNO3
C6H5CHO
Benzaldehyde
2H2O
C6H5CHCl2
C6H5CH
H2O
C6H5CHO
OH
(unstable)
OCOH
Ca + Ca
C6H5COO
OCOH
Calcium benzoate
(calcium formate)
2C6H5CHO + 2CaCO3
18.5.1 Properties :
Colourless liquid with boiling point 452 K. It has the smell of bitter
almond and known as oil of bitter almonds.
Chemical Properties :
C6H5
C=O
H
It resembles aliphatic aldehydes in many properties.
Because of the presence of benzene ring the reactivity towards
nucleophilic attack on carbonyl carbon is decreased.
Absence of -hydrogen atom indicates that a carbanion cannot be
generated at the -carbon. So aldol type of condensation cannot be
expected.
256
C6H5CHO
C6H5COOH
C6H5CHO
C6H5CH2OH
C6H5CHO
C6H5CH3
or
N2H4 / KOH
C6H5CH
NHR
OH
C6H5CH=O + C6H5NH2
C6H5CH
[H2O]
[H2O]
NHC6H5
C6H5CH=NR
C6H5CH=NC6H5
C6H5 C = O
C6H5 C = O
|
|
H Cl Cl
Cl
HCl
C6H5CHO + C6H5CHO
C6H5COONa + C6H5CH2OH
Benzaldehyde Benzaldehyde
Sodium benzoate
Benzyl alcohol
The mechanism involves the transfer of hydride ion from one molecule
of benzaldehyde to the other molecule.
I step.
H
|
C6H5 C = O
OH
H
|
C6H5 C O
|
OH
.H|.
H
|
C6H5 C = O + C6H5 C O
|
|
H
OH
C6H5 C O + C6H5 C = O
|
|
OH
H
H
|
C6H5 C = O + C6H5 C OH
|
|
O
H
H
|
C6H5 C = O + C6H5 C O
|
|
OH
H
The benzyloxide ion picks up the acidic proton from benzoic acid to
give benzyl alcohol.
258
CH3CHO
CH2CHO (Carbanion)
H+
NaOH
C6H5CH = O
()CH
C6H5
2CHO
CHO
C6H5CHOH
|
CH2CHO
|
CH2CHO
(Nucleophilic attack)
C6H5 CH OH
|
CH H
|
CHO
C6H5 CH
||
CH CHO
-elimination
H2O
(Cinnamaldehyde)
Similarly,
NaOH
C6H5CHO + CH3COCH3
C6H5CH = CHCOCH3
alc
KCN
259
O
||
C6H5CHOH C C6H5
(Benzoin)
C6H5CH = O + CH 3COOCOCH3
Acetic anhydride
C6H5CH = CHCOOH
Cinnamic acid
+
CH3COOH
Sodium acetate is the base that generates a carbanion at the -carbon in
the acetic anhydride. This brings forth nucleophilic attack on the carbonyl
carbon forming -hydroxy acid, water gets removed from this by
-elimination.
12. Knoevenagal reaction :
C6H5CH = O + H2C(COOH)2
C6H5CH = C(COOH)2
Malonic acid
CO2
C6H5CH=CHCOOH
(Cinnamic acid)
260
Nitration :
CHO
CHO
Conc. HNO3
Conc. H2SO4
NO2
Sulphonation :
CHO
CHO
Conc. H2SO4
SO3H
+
(The electrophile SO3H)
N(CH3)2
Conc. H2SO4
CH=O
H
N(CH3)2
CH
N(CH3)2
N(CH3)2
Halogenation :
CHO
CHO
Cl2
FeCl3
Cl
(FeCl3 is the Lewis acid catalyst that forms the electrophile Cl+)
261
Reactions
HCHO
CH3CHO
1. Iodoform test
gives iodoform
2. With Ammonia
forms urotropine
a condensation product
gives simple
addition product.
3. With alkaline
solution
undergoes Cannizzaro
reaction
undergoes aldol
condensation.
4. With phenol
forms thermosetting
plastic-bakelite
5. With RMgX
forms RCH2OH
RCHOH is formed.
|
CH3
Reactions
CH3CHO
C6H5CHO
1. Heating with
gives a red precipitate
Fehlings solution.
no reaction.
2. With ammonia
forms complex
condensation
product.
3. With caustic
soda
undergoes Aldol
condensation
undergoes Cannizzaro
reaction.
4. With primary
amines
does not
form Schiffs base
5. With chlorine
does not
form acetyl chloride
forms benzoyl
chloride.
6. Polymerisation
undergoes
polymerisation.
7. Electrophilic
substitution.
does not
undergo.
undergoes at the
meta position.
8. With Schiffs
reagent.
262
Uses
Benzaldehyde is used
(a) In the preparation of cinnamaldehyde, cinnamic acid and mandelic acid.
(b) Benzoin prepared from benzaldehyde is used as tincture benzoin in
medicine for throat infection.
(c) With phenols and aromatic tertiary amines, it forms triphenyl methane
dyes.
(d) In perfumery, as a flavouring agent.
Questions.
(O)
(CH3)2C = O
K2Cr2O7/H+
(Calcium acetate)
CH3
Distillation
H3C
C = O + CaCO3
(Acetone)
263
573 K
(CH3 )2 C = O
Cu
H2
Acetone
(Isopropyl alcohol)
Cl
2 NaOH
CH3
C
CH3
OH
C
CH3
Cl
(Isopropyl alcohol)
OH
(Unstable)
H2O
CH3
C=O
CH3
Acetone
18.6.1 Properties :
CH3COCH3
CH3COOH
H3C
LiAlH4
C=O
H3C
H()
H3C
H3C
CO
|
H
H2O
H3C
H3C
alkoxideion
COH
|
H
isopropyl alcohol
Zn/Hg/HCl (or)
H3C
N2H4/NaOC2H5
H3C
CH2
(Acetone)
(Propane)
5. Haloform reaction
The compounds having CH3CHOH or CH3CO group undergoes
haloform reaction.
It undergoes halogenation at -carbon atom.
CH3COCH3 + 3 Cl2
CH3C = O
|
CH3
+ HNH2 (Ammonia)
HCH2COCH3
NH2
CH3CCH2 COCH3
|
CH3
(Diacetone amine)
265
KOH
CH3
|
CH3 C CCl3
|
OH
(Chloretone)
9. With dry hydrogen chloride first it forms mesityl oxide and then phorone.
This reaction follows aldol type condensation followed by dehydration.
H3C
Dry. HCl
C = O + H2CHCOCH3
H3C
C = CHCOCH3
H2O
H3C
H3C
H3C
Mesityl oxide
4-methyl pent-3-ene-2-one
CH3
C = CHCOCH3 + O = C
H3C
CH3
H3C
CH3
C=CH.COCH=C
H2O
H3C
CH3
Phorone
2,6-dimethyl hept-2,5-diene-4-one
Conc. H2SO4
3CH3COCH3
+
CH3
3 H2O
CH3
18.6.2 Uses.
266
Reactions
CH3CHO
CH3COCH3
1. With Fehlings
solution.
gives a red
precipitate
2. With Tollens
reagent.
3. Oxidation
4. Reduction with
NaBH4
ethanol (primary
alcohol)
isopropyl alcohol
(secondary alcohol)
5. With NH3
simple addition
forms complex
product is formed. ketonic amine.
6. Iodoform
reaction
forms iodoform
and formic acid.
7. Polymerisation
pink colour
appears in cold.
no pink colour in
cold.
9. Warming with
NaOH
a brown resinons
mass.
no resinous mass.
forms iodoform
and acetic acid.
Formula
Common name
IUPAC name
CH3COC6H5
acetophenone
C6H5COC6H5
diphenyl ketone
benzophenone
18.7.1 ACETOPHENONE
Preparation
+ ClCOCH3
COCH3
AlCl3
+ HCl
Acetyl chloride
Acetophenone
Benzene
COOCH3
Ca
Ca
C6H5COO
CaCO3+ C6H5COCH3
COOCH3
(Calcium acetate)
Acetophenone
(Calcium acetate)
18.7.2 Properties
(O)
C6H5COCOOH
(Acetophenone)
C6H5COOH+CO2
benzoic acid
C6H5COCH3
2(H)
C6H5CHOHCH3
4(H)
C6H5CH2CH3 + H2O
268
Halogenation :
C6H5COCH2 Br + HBr
Phenaceylbromide
CH3COC6H5
NaOH
CHCl3
C6H5COONa
Electrophilic substitution :
Acetyl group deactivates the benzene ring and is meta directing group.
Nitration :
COCH3
COCH3
HNO3
H2SO4
NO2
m-nitroacetophenone
18.7.3 Uses
Diphenyl ketone
O
||
C6H5 C C6H5
269
COC6H5
anhyd.
AlCl3
ClCOC6H5
HCl
C6H6 + Cl CO Cl + C6H6
C6H5COC6H5
Benzene +
Benzophenone
Phosgene
+ Benzene
Distillation
C6H5COC6H5 + CaCO3
Benzophenone
(Calcium Benzoate)
18.8.1 Properties
(O)
C6H5COOH
Benzoic acid
270
2(H)
Benzophenone
C6H5CHOHC6H5
diphenyl carbinol
C6H5COC6H5
C6H5CH2C6H5
Benzophenone
diphenyl methane
C6H5 COOK
Potasium benzoate
C6H6
Benzene
18.8.2 Uses :
SELF EVALUATION
(A) Choose the correct answer :
271
3. Isopropyl alcohol vapours with air over silver catalyst at 520 K give
(a) tert.butyl alcohol
(b) acetaldehyde
(c) acetone
(d) 2-propanol
4. Methyl ketones are usually characterised by
(a) the Fehlings solution
(b) the iodoform test
(c) the Schiffs test
(d) the Tollens reagent
5. Which of the following compounds is oxidised to give ethyl methyl
ketone ?
(a) 2-propanol
(b) 2-pentanone
(c) 1-butanol
(d) 2-butanol
6. Formaldehyde polymerises to give
(a) paraldehyde
(b) paraformaldehyde
(c) formalin
(d) formic acid
7. Tollens reagent is
(a) ammoniacal cuprous chloride (b) ammoniacal cuprous oxide
(c) ammoniacal silver nitrate
(d) ammoniacal silver chloride
8. When acetaldehyde is heated with Fehling solution, it gives a precipitate of
(a) Cu2O
(b) CuO
(c) CuO + Cu2O
(d) Cu
9. The compound that does not undergo Cannizzaro reaction is
(a) formaldehyde
(b) acetaldehyde
(c) benzaldehyde
(d) trimethyl acetaldehyde
10. The formation of cyanohydrin from a ketone is an example of
(a) electrophilic addition
(b) nucleophilic addition
(c) nucleophilic substitution (d) electrophilic substitution
11. Hydrogenation of benzoyl chloride in the presence of Pd on BaSO4
gives
(a) phenol
(b) benzoic acid
(c) benzyl alcohol
(d) benzaldehyde
12. From which of the following, tertiary butyl alcohol is obtained by the
action of methyl magnesium iodide ?
(a) HCHO
(b) CH3CHO
(c) CH3COCH3
(d) CO2
272
13. During reduction of aldehydes with hydrazine and C2H5ONa the product
formed is
(a) RCH = NNH2
(b) RC N
(c) R C NH2
(d) RCH3
||
O
14. Aldol is
(a) 2-hydroxy butanol
(b) 3-hydroxy butanol
(c) 3-hydroxy butanal
(d) 2-hydroxy butanal
15. In the reduction of acetaldehyde using LiAlH4 the hydride ion acts as
(a) electrophile
(b) nucleophile
(c) both (a) and (b)
(d) a free radical
16. Which of the following statement is wrong ?
(a) 2-pentanone and 3-pentanone are position isomers
(b) aqueous solution of formaldehyde is known as formalin
(c) aldehydes and ketones undergo nucleophilic substitution
(d) aldehydes act as reducing agents
17. A cyanohydrin of a compound X on hydrolysis gives lactic acid. The X
is
(a) HCHO
(b) CH3CHO (c) (CH3)2 CO (d) C6H5CH2CHO
18. The IUPAC name of CH3 C = CH C CH3 is
|
||
CH3
O
(a) 4-methylpent-3-en-2-one
(b) 2-methylpent-3-en-2-one
(c) 3-methyl pent-2-en-1-one
(d) None of these
19. Which of the following does not give iodoform test ?
(a) aceto phenone
(b) benzophenone
(c) CH3 CHOH
(d) CH3 CH CH2 CH2 CH3
|
|
CH3
OH
20. The compound which does not reduce Fehling solution is
(a) formaldehyde
(b) acetaldehyde
(c) benzaldehyde
(d) propionaldehyde
273
Conc. H2SO4
21. CH3COCH3
The product is
(a) mesitylene
(b) mesityl oxide
(c) phorone
(d) paraldehyde
22. Which compound on strong oxidation gives propionic acid ?
(a) CH3 CH CH3
(b) CH3 CO CH3
|
OH
(c)
CH3
|
CH3 C OH
|
CH3
(A)
LiAlH4
(B)
SOCl2
(C)
alc.KOH
Acetone
Answers (B)
OH
|
CH3 CH CH3 :
Isopropyl alcohol
Cl
|
(C) CH3 CH CH3 : Isopropyl chloride
(D) CH3 CH = CH2 : propylene
14. How will you synthesise acetaldehyde from formaldehyde ?
276
(D)
Answers :
O
||
H CH
CH3MgBr
H2O/H+
CH3CH2OH
K2Cr2O7
ethyl alcohol
H2SO4
CH3CHO
acetaldehyde
formaldehyde
O
||
CH3 CH2 CH2 C ONa
+ CHI3 + 3H2O + 3NaI
Iodoform
(yellow precipitate)
CH3MgI
acetaldehyde
OH
|
CH3 CH CH3
isopropyl
alcohol
K2Cr2O7
H2SO4
O
||
CH3 C CH3
acetone
and
NaOH
19. Write the structural formula of the main product formed when ; (i) The
compound obtained by hydration of ethyne is treated with dilute alkali.
(ii) Methanal reacts with ammonia.
Hg2+
Ethyne
OH
CH3CHO
Ethanal
(CH2)6 N4 + 6H2O
278
CH3COOH
CH3CH2CH3
CH3CH2CH3
CH2 = CH2
279
SUMMARY :
Functional group of aldehyde and ketone.
Structure, isomerism involved and nomenclature - common name and
IUPAC name.
Preparation - by the oxidation or dehydrogenation of alcohols ozonolysis
of olefins, hydration of alkynes, catalytic reduction of acid chloride, distillation
of calcium salt of fatty acid and hydrolysis of gem dihalide.
Properties - Higher boiling point of polar molecules than hydro carbons
- carbon of the carbonyl group is the site of nucleophilic attack - Most of the
addition reactions - nucleophilic - addition product eliminates water forming
condensation product. Reactions with NaHSO3, HCN, NH3 , RMgX,
NH2OH, C6H5NHNH2, NH2NHCONH2, reductions with NaBH4, LiAlH4,
also nucleophilic in nature, that give alcohols.
Some reductions - Zn/Hg/HCl or heating with N2H4/NaOC2H5 - gives
hydrocarbon.
Mild oxidising agents like Fehlings solution, Tollens reagent - oxidise
aldehydes to mono carboxylic acids. Ketones require more powerful oxidising
agents like acidified K2Cr2O7 or KMnO4 in which carbon-carbon bond is
cleaved to give carboxylic acids having lesser number of carbon atoms.
Aldehydes and ketones having -hydrogen atom form carbanions in
presence of base. These take part in condensation reactions with other
carbonyl compounds. Aldehydes and ketones having CH3CO- group undergo
haloform reaction.
Formaldehyde undergoes condensation with Ammonia to form
urotropine and phenol to form Bakelite.
Acetone and acetaldehyde undergo aldol condensation while
formaldehyde undergoes Cannizaro reaction.
Distinction between formaldehyde and acetaldehyde and acetaldehyde
and acetone.
Structure and nomenclature of aromatic aldehydes - preparation and
properties - Reactivity of carbonyl group - decreased by benzene ring.
280
281
are
OH
called carboxylic acids. The acid may be monocarboxylic acid, if it contains
one COOH group ; a dicarboxylic acid if it contains two COOH groups ;
a tricarboxylic acid if it contains three COOH groups etc.
The aliphatic mono carboxylic acids are called fatty acids and the higher
members like Stearic acid (C17H35COOH), palmitic acid (C15H31COOH),
oleic acid (C16H33COOH) etc., occur as glycerides in oils and fats.
Nomenclature :
(a) Trivial system :
The names of lower members are derived from the source of individual
acids.
Formula
HCOOH
CH3COOH
C3H7COOH
C4H9COOH
C11H23COOH
Source
Red ant (formica)
Vinegar (acetum)
Butter (Butyrum)
Root of valarion plant
Laurel oil
Trivial name
formic acid
acetic acid
butyric acid
valeric acid
lauric acid
Derived names :
Sometimes fatty acids are named as alkyl derivatives of acetic acid.
(e.g.,) MeCH2COOH
Me2CHCOOH
Me2CH.CH2COOH
IUPAC names :
Acids are named after the alkane by replacing the ending e by oic
acid.
HCOOH
Methanoic acid
CH3COOH
Ethanoic acid
CH3CH2COOH
Propanoic acid
CH3CH2CH2COOH
Butanoic acid
CH3CH2CH2CH2COOH
Pentanoic acid
In case of substituted acid the longest carbon chain including the carboxyl
group is taken as the parent chain.
Position of the substituent is indicated by either 1, 2, 3, etc., (or) , ,
, ...
When it is done by numbers the carbon of the carboxyl group is numbered
as (1) when it is done by Greek letters the carbon next to the COOH group
.
is designated as
CH3
|
1
CH3 CH2 CH COOH
4
283
Isomerism :
1. Chain isomerism :
This arises due to the difference in the carbon chain of alkyl group
attached to carboxyl group.
CH3
|
CH3 CH2 CH2 CH2 COOH
CH3 CH CH2 COOH
(pentanoic acid)
2. Functional isomerism :
Carboxylic acids may be functional isomers of esters.
CH3 CH2 COOH
and
CH3 COOCH3
propanoic acid
methyl acetate
HCOOC2H5
ethyl formate
(O)
(O)
C=O
R
(i)
RCOOH
(O)
RCOOH
R
CH3CH2OH
(O)
ethyl alcohol
(ii)
(O)
RCHO
CH3
CHOH
CH3CHO
(O)
CH3COOH
acetaldehyde
(O)
CH3
acetic acid
(O)
C=O
CH3
CH3
Isopropyl alcohol
acetone
CH3COOH + CO2
acetic acid
284
2. Hydrolysis methods :
(a) Hydrolysis of cyanides, amides and esters : Alkyl cyanides, amides,
esters are hydrolysed with aqueous acid or alkali to give carboxylic acid.
RCN
(i)
R C NH2
||
O
O H2
alkyl cyanide
CH3 C N
RCOOH
amide
CH3 C NH2
||
H2O
methyl cyanide
H2O
H2O
CH3COOH + NH3
O
acetamide
HCN
H2O
Hydrogen cyanide
HC=O
|
NH2
H2O
H C OH + NH3
||
O
Formamide
(ii)
O
||
R C NH2
H2O
RCOOH
NH3
HO H
Example,
O
||
CH3 C NH2
O
||
CH3 C OH + NH3
H2O
acetamide
(iii)
O
||
R C OCH3
ester
H+
or
O
||
R C OH
CH3OH
O
||
CH3 C OH
CH3OH
OH
HO H
Example,
O
||
CH3 C OCH3
methyl acetate
HOH
H+ or OH
acetic acid
OH
R C OH
OH
3KOH
H2O
unstable
CH3 CCl3
OH
CH3 C OH
OH
3KOH
trichloro ethane
H2O
RC=O
|
OH
CH3 C = O
|
OH
RMgI + CO2
+H2O
O
||
OH
RCOH + Mg
I
CH3MgI + CO2
O
||
H2O
CH3 C OMgI
O
||
OH
CH3 C OH + Mg
I
3(O)
(O)
HCOOH
HCOOH
286
5. From glycerol
By heating glycerol with oxalic acid at 373 K 383 K
CH2 OH
|
+ HO C = O
CHOH
|
|
COOH
CH2OH
O
||
CH2 O CH
|
CHOH
|
CH2OH
CH2 O CO COOH
|
CO2
CHOH
|
CH2OH
383 K
CH2OH
|
CHOH +
|
CH2OH
H2O
glycerol monoformate
HCOOH
formic acid
19.2.1 Properties
1. Lower members are pleasant smelling liquids with higher boiling points.
The higher members are waxy solids. The higher boiling points are
explained on the basis of association by hydrogen bonding.
O
HO
RC
CR
O
OH
2. The first few members are highly soluble in water and higher members
are insoluble. This can also be explained on the basis of hydrogen bonding
between acids and water. With higher members the size of the alkyl group
is increased which repels the hydrophilic groups.
Chemical Properties :
1. Fatty acids react with alkalies to form salt and water and liberates CO2
with carbonates (stronger than carbonic acid).
CH3COOH
NaOH
CH3COONa
287
H2O
2 HCOOH
+ 2Na2CO3
2 HCOONa
(sodium formate)
+ H2O + CO2
2. They liberate hydrogen, when react with electropositive metals like zinc
or magnesium.
2CH3COOH
Zn
(CH3COO)2 Zn
H2
H2
(zinc acetate)
2HCOOH
Mg
(HCOO)2 Mg
(magnesium formate)
CH3COOH + C2H5OH
CH3COOC2H5
H2O
(ethyl acetate)
H+
HCOOH
+ CH3OH
HCOOCH3
(methyl formate)
H2O
Mechanism of esterification
Protonation of the OH group of the acid, enhances the nucleophilic
attack by alcohol to give the ester.
H+
CH3 CO O
H
288
CH3 CO O
H
|+
O C2H5
H
| +
CH3 C O
|
H
O
..
C2H5 OH
H+ / H2O
OC2H5
|
CH3 C
||
O
4. Dehydration
Except formic acid others undergo intermolecular dehydration on heating
with P2O5 forming anhydride.
CH3 CO O H
+
CH3 CO OH
P2O5
CH3 CO
O
CH3 CO
(Acetic anhydride)
Con. H2SO4
H2O
CO
HO
5. With phosphorous pentachloride or thionyl chloride.
(i) Acid chloride is formed.
O
O
||
||
CH3 C O H
CH3 C + POCl3 + HCl
|
Cl PCl3 Cl
Cl
acetic acid
(acetyl chloride)
289
HC=O
|
Cl
Cl PCl3 Cl
POCl3
CO
HCl
formyl chloride
HC=O
HCl
Cl
The carboxyl group is involved in resonance.
O()
O
C
C
O
()
>
H2/Ru-pressure
or
R CH2 OH
LiAlH4
HI/P
CH3 CH3
290
RCOONa
RH + Na2CO3
(Hydrocarbon)
NaOH/CaO
CH3COONa
CH4
sodium acetate
methane
Na2CO3
160oC
H2
CO2
HO
H+
O()
R
C
RH
CO2
alkane
O
Carboxylate anion
8. Halogenation :
(i) Fatty acids having -hydrogen atoms, can be converted to -halo acids
by halogen in presence of halogen carrier like red phosphorous.
Br2/P
CH3CH2COOH
propionic acid
CH3CHBr COOH
CH3CBr2COOH
, , di bromopropionic acid
(ii) HVZ - reaction : When the halogenation is carried out with halogen
and phosphorous trihalide, this reaction is known as Hell-Volhard
Zelinsky reaction. (HVZ-reaction).
Br2/PBr3
RCH2COOH
H2O
RCH2COBr
RCHBrCOBr
RCHBrCOOH
RCOONH4
(Ammonium Salt)
HCOOH + NH3
HCOONH4
H2O
RCONH2
(Amide)
P2O5
RCN
H2O (Cyanide)
HCONH2
(Formamide)
CH3 COO Na
CH3
|
+ 2CO2 + 2Na
CH3
sodium
CH3 COO Na
ethane
CH3COCH3 + CaCO3
acetone
Calcium acetate
(a) Formic acid reduces ammoniacal silver nitrate solution (Tollens reagent)
to metallic silver.
HCOOH + Ag2O
(b) Formic acid reduces Fehlings solution. It reduces blue coloured cupric
ions to red coloured cuprous ions.
HCOO
+ 2Cu2+ + 5OH
(blue)
(red)
360oC
H COONa
COONa
|
COONa
Sodium formate
Sodium oxalate
H2
CH2(OH)CH2COOH
-hydroxy propionic acid
C6H12O6
BAL
H2O
C6H12O6
(glucose)
2CH3COCHO
Methyl glyoxal
294
+ C6H12O6
(fructose)
2CH3CHOHCOOH
Lactic acid
electric
CHCH
Arc
1%Hg
80
dil. HCl
CH3CH(OH)CN
dil. H2SO4
CH3CHO
HCN
CH3CH(OH)COOH
lactic acid
CH3CH = CH2
dil/NaOH
CH3CHCl CH2Cl
propylene
CH3CH(OH)CH2OH
1,2-dichloro propane
(O)
propane 1,2-diol
CH3CH(OH)COOH
lactic acid
Ag2O
H2O
2CH3CH(OH)COOH
lactice acid
Properties :
Colourless syrupy liquid, hygroscopic and extremely soluble in water.
Chemical properties :
Reactions characteristic of both OH and COOH group.
295
1. Oxidation :
(i) Mild oxidising agent like Fentons reagent Fe2+/H2O2 forms pyruvic
acid with lactic acid
CH3CH(OH)COOH
(O)
CH3COCOOH
H2O2/Fe2+
Lactic acid
Pyruvic acid
CH3CH(OH)COOH
CH3CHO + HCOOH
3. Haloform reaction :
It undergoes haloform reaction with I2 and caustic soda.
(O)
CH3CH(OH)COOH
CH3COCOOH
I2
pyruvic acid
NaOH
CHI3 +
iodoform
CI3COCOOH
tri iodo pyruvic acid
(COONa)2
sodium oxalate
4. With PCl5
With PCl5 it forms lactyl chloride.
CH3CH(OH)COOH + PCl5
CH3 CH COCl
|
Cl
lactyl chloride
O=C
HC CH3
O=C
OH H O
CHCH3
O
lactide
296
In tanning industry.
In soft drinks.
In the treatment of digestive disorder in children.
Preparation of lactates, ethyl lactate as a solvent.
Silver lactate as an antiseptic and astringent.
where n = 0, 1, 2, 3, etc.
Common name
IUPAC name
HOOC COOH
Oxalic acid
Malonic acid
HOOC(CH2)2COOH
Succinic acid
Adipic acid
HNO3
V2O5
COOH
|
COOH
+ 5H2O
2HCOONa
sodium formate
NaOOC COONa
sodium oxalate
H2
COO
|
Ca +
COO
+ Ca(OH)2
sodium oxalate
2 NaOH
calcium oxalate
COO
|
Ca + H2SO4
COO
COOH
|
COOH
+ CaSO4
oxalic acid
[O]
COOH
|
COOH
glycol
4. From Cyanogen :
By passing cyanogen through an aqueous solution of acid or alkali.
CN
|
CN
cyanogen
2H2O
CONH2
|
CONH2
oxamide
298
2H2O
COOH
|
COOH
2NaCN
Ethylene
di bromide
CH2CN
|
CH2CN
H2O
HCl
ethylene
dicyanide
CH2COOH
|
CH2COOH
succinic acid
19.4.2 Properties
Oxalic acid occurs as potassium hydrogen oxalate in the wood sorrel,
and tomatoes. The insoluble calcium oxalate is found in some stony deposits
in kidneys and bladder in human body. Oxalic acid is an active poison
depressing the central nervous system.
Chemical Properties
Dicarboxylic acid gives all the usual reactions of COOH group twice.
1. With alkali : With NaOH it gives two kinds of salts.
(e.g.,)
(i) COOH
|
+ NaOH
COOH
oxalic acid
(ii) CH2COOH
|
+ NaOH
CH2COOH
COONa
|
COOH
COONa
|
COONa
NaOH
mono sodium
oxalate
CH2COONa
|
CH2COOH
Succinic acid
mono sodium
succinate
disodium
oxalate
NaOH
CH2COONa
|
CH2COONa
disodium succinate
299
COOH
|
COOH
COONH4
|
COONH4
+ 2NH3
CONH2
|
+ 2H2O
CONH2
ammonium
oxalate
oxamide
CH2COONH4
|
CH2COONH4
Succinic acid
Ammonium succinate
CH2CO
|
NH
CH2CO
Succinimide
3. With PCl5 :
With PCl5, these form the acid chlorides.
(i) COOH
|
+
COOH
COCl
|
COCl
PCl5
oxalic acid
CH2COOH
|
+
CH2COOH
oxalylchloride
POCl3
CH2COCl
|
+
CH2COCl
PCl5
H2O
phosphorous
oxy chloride
POCl3
H2O
succinoyl chloride
4. Action of heat :
(i) Oxalic acid on heating at 373 K 378 K loses water of hydration. On
further heating it decomposes to formic acid and carbon dioxide.
COOH
|
COOH
473K
HCOOH
formic acid
+ CO2
300oC
CH2 CO
|
O
CH2 CO
H2O
300
2CO2
+ [O]
+ H2O
Uses :
Oxalic acid is used
1. for removing ink stains and iron stains.
2. as mordant in dyeing and calico printing.
3. in manufacture of ink and metal polishes.
4. Redox titration
Succinic acid is used :
1. in the manufacture of lacquers and dyes.
2. It is a very important laboratory reagent.
19.5 STRENGTH OF CARBOXYLIC ACIDS
An acid is a proton donor. The base with which a proton can be released
determines the strength of an acid. Organic acids are weak acids. Greater
the stability of the anion of the acid, higher is its strength. Thus, for a
carboxylic acid, say acetic acid.
H
H
H
|
O
|
O
|
O
H CC
H CC
H CC
|
O
|
O
|
OH
H
H
H
Acid
Anion
+ H3O+
When the bonding pair of electrons between oxygen and hydrogen in
OH group, is shifted towards oxygen, easier the hydrogen is released as a
proton.
Thus when chloroacetic acid is taken, the (I) effect of chlorine increases
its strength.
301
H
|
C
|
H
Cl
O
C
O
O
>>
Cl2CHC
OH
O
>
ClH2C
OH
OH
On the other hand comparing the strength of carboxylic acids they vary
as follows :
CH3CH2 COOH <
propionic acid
CH3COOH
<
acetic acid
HCOOH
formic acid
Since alkyl groups are +I groups, they increase the strength of the
OH bond making the release of hydrogen difficult. (i.e.,) it becomes a
weak acid.
In the case of aromatic acids, presence of chlorine, nitro group, carbonyl
group especially at ortho position increases its strength due to I effect.
COOH
COOH
O2N
COOH
Cl
OHC
>
>
CH3
COOH
OH
COOH
Benzoic acid
o-toluic acid
NH2
COOH
salicylic acid
(o-hydroxy benzoic
acid)
COOH
anthranilic acid
(o-amino benzoic
acid)
CH3
Toluene
Ethyl
benzene
CH2Cl
Benzyl
chloride
CH2OH
Benzyl
alcohol
Benzaldehyde
H+/KMnO4
C6H5COOH
NaOH
(ii) C6H5CH2Cl
C6H5CH2OH
H+/KMnO4
(iii) C6H5CHO
C6H5COOH
303
Benzoic acid
(O)
KMnO4
CHO
C6H5COOH
H+
H+
(C6H5CONH2)
H2O
Benzamide
C6H5COOH
H2O
H2O
C=O
BrMgO
Br
C6H5C = O + Mg
|
OH
OH
19.6.2 Properties
Physical properties
White crystalline solid-soluble in hot water, alcohol and ether and slightly
soluble in cold water.
Chemical Properties
Reactions of both COOH group and benzene ring.
1. Acidic properties :
(a) Benzoic acid dissolves in NaOH and NH4OH forming salts.
C6H5COOH
+ NaOH
C6H5COONa + H2O
(sodium benzoate)
C6H5COOH + NH4OH
C6H5COONH4
(Ammonium benzoate)
H2O
C6H5CONH2
H+
C6H5COOC2H5
(ethyl benzoate)
304
+ H2O
2. Replacement of OH group.
By the action of phosphorous pentachloride or thionyl chloride, benzoyl
chloride is formed.
C6H5COOH + PCl5
C6H5COOH + SOCl2
Thionyl chloride
3. Decarboxylation :
Heating with sodalime gives benzene.
C6H5COOH
NaOH
CaO
soda lime
C6H6
CO2
4. Reduction :
Lithium Aluminium hydride reduces Benzoic acid to Benzyl alcohol.
O
C6H5C
LiAlH4
LiAlH4
[C6H5CHO]
OH
C6H5CH2OH
Benzyl alcohol
Benzoic acid
COOH
HNO3
H2SO4
NO2
m-nitro benzoic acid
305
6. Chlorination :
COOH
COOH
Cl2
FeCl3
Cl
m-chloro benzoic acid
COOH
Fuming
H2SO4
SO3H
m-sulphonyl benzoic acid
OH
COOH
COOH
(o-hydroxy benzoic acid)
COOH
(p-hydroxy benzoic acid)
19.7.1 Preparation :
Salicylic acid can be prepared by heating phenol with NaOH to get
sodium phenoxide.
306
OH
ONa
NaOH
OH
CO2
403K/pressure
COONa
Mechanism :
O
O
||
C
||
O
OH
C
O
OH
COONa
COOH
HCl
+ NaCl
(Salicylic acid)
19.7.2 Properties
Physical Properties
It is a white crystalline solid - soluble in hot water, ethanol and ether.
Test for salicylic acid :
1. An aqueous solution of salicylic acid gives violet colour with neutral
ferric chloride.
2. It gives effervescence with the sodium bicarbonate.
3. It is soluble in sodium hydroxide and reprecipitated on acidification.
307
4. With Bromine water the colour is discharged with the formation of white
precipitate.
Mechanism :
Reaction of bromine with salicylic acid.
O
OH
+OH
C
O
Br
Br Br
OH
+OH
+ Br
Br
+ CO2
O
Br
OH
Br
Br
OH
Br
2Br2
Br
Chemical Properties :
Properties of phenolic function.
OCOCH3
(CH3CO)2O
COOH
COOH
Acetyl salicylic acid or Aspirin
308
OH
Br2
COOH
Br
Br2
OH
Br
CO2
Br
(2,4,6 Tribromo phenol)
OH
+ CO2
+ NaHCO3
COOH
H2O
COONa
(sodium salicylate)
OH
HCl
COONa
COOH
2. With CH3OH
On heating with methyl alcohol in presence of con. H2SO4 a pleasant
smelling liquid-methyl salicylate is formed.
OH
OH
CH3OH
COOH
H2SO4
+
COOCH3
(Methyl salicylate)
309
H2O
Methyl salicylate is present in the oil of winter green and other essential
oils.
19.7.3 Uses
Salicylic acid is used (i) It is an antiseptic and disinfectant (ii) as a food
preservative (iii) as a medicine for rheumatic pain, (iv) in the manufacture of
aspirin, salol, methyl salicylate, (v) in the preparation of azo dyes.
19.8 FUNCTIONAL DERIVATIVES OF CARBOXYLIC ACID :
O
||
RCY
Functional group
Example
OH
Carboxylic acid
CH3COOH
acetic acid
halogen
acid halide
CH3COCl
acetyl chloride
OCOR
acid anhydride
CH3COOCOCH3
acetic anhydride
OR
ester
CH3COOC2H5
ethyl acetate
NH2
amide
CH3CONH2
acetamide
310
O
Cl
CH3 C
O
H
+
OH
HCl
(gas)
Chemical Properties :
1. It is a powerful acetylating agent, a reagent that introduces CH3CO group, especially with compounds containing OH group or NH group.
O
O
||
||
(i) H O H + Cl C CH3
H O C CH3 + HCl
..
acetic acid
(ii) C2H5OH
..
(iii)
O
||
+ Cl C CH3
CH3
..
C6H5 OH +
Cl
O
||
C2H5OCCH3 + HCl
ethyl acetate
C=O
CH3COOC6H5
Phenyl acetate
COCH3
+ CH3COCl
anhy. AlCl3
+ HCl
(Acetyl chloride)
+ CH3COONa
(Sodium acetate)
CH3COOCOCH3 + NaCl
(Acetic anhydride)
P2O5
CH3COO H
CH3CO
O + H2O
CH3CO
(Acetic anhydride)
1.
CH3CO
CH3CONH2+ CH3COOH
(Ammonolysis)
(Acetamide)
CH3CO
.. +
H 2N H
ammonia
2.
CH3CO
CH3COOH + CH3COCl
O + H Cl
acetyl chloride
CH3CO
CH3CO
O
CH3CO
Cl
|
PCl3
|
Cl
2CH3COCl + POCl3
acetylchloride
H2SO4
CH3COOCH3 + H2O
Methyl acetate
313
CH3COCl + CH3OH
CH3COOCH3 + HCl
CH3COOCOCH3 + CH3OH
CH3COOCH3 + CH3COOH
H+/H2O
CH3COOH + CH3OH
CH3COOCH3 + NaOH
CH3COONa + CH3OH
sodium acetate
(Saponification)
2. Alcoholysis : In presence of a little acid, methyl acetate is cleaved by
ethyl alcohol to form ethyl acetate.
H+
CH3COOCH3 + C2H5OH
This is called trans esterification.
CH3COOC2H5 + CH3OH
CH3COOCH3 + NH3
CH3CONH2 + CH3OH
C2H5ONa
CH2COOCH3 +
CH3
H+
CH3
C=O
C=O
CH3O
CH2COOCH3
+ OCH3
Methyl acetoacetate
CH2COOCH3
314
Acetamide
Preparation of acetamide
1. By heating ammonium acetate
CH3COONH4
CH3CONH2 + H2O
CH3CONH2 + HCl
CH3CONH2 + CH3COOH
Acetic anhydride
CH3CONH2 + CH3OH
Methyl acetate
H2O2
CH3CONH2
NaOH
H
|
HN
CH3 C
C CH3
NH
|
H
315
CH3CONH2
H+
CH3COOH + NH3
H2O
(b)
CH3CONH2
(acetic acid)
NaOH
CH3COONa + NH3
(Sodium acetate)
2. With HCl
It is feebly basic, forms unstable salt with strong inorganic acid.
CH3CONH2 + HCl
CH3CONH2 . HCl
(amide hydrochloride)
P2O5
H2O
CH3CN
Br2
NaOH
CH3NH2 + CO2
SELF EVALUATION
(A) Choose the correct answer :
1. Which of the following is least acidic
(a) C2H5OH
(c) C6H5OH
(b) CH3COOH
(d) ClCH2COOH
(b) Phenol
(d) Acetylene
(b) ethane
(d) benzene
CH3
|
6. The IUPAC name of CH3 CH2 CH COOH is
(a) -methyl butric acid
(c) 2-methyl butanoic acid
(b) position
(d) functional
(a) CH3COCOOH
(b) CH3CH2COOH
(d) COOHCH2COOH
(c) CH3CHOHCHO
19. The compound found in some stony deposit in kidneys is
(a) potassium oxalate
(b) oxalic acid
(c) potassium succinate
(d) calcium oxalate
20. Ethylene cyanide on hydrolysis using acid gives
(a) oxalic acid
(b) succinic acid
(c) adipic acid
(d) propionic acid
(B) Answer in one or two sentences :
1. What are carboxylic acids ?
2. Give the source and trivial names of
(i) C3H7COOH and (ii) HCOOH.
3. How is the conversion of acetonitrile to acetic acid effected ?
4. Boling point of carboxylic acids are higher than those of alcohols of
same molecular mass - reason out.
5. Formic acid reduces Tollen's reagent, but acetic acid does not-Give
reasons.
6. Write two tests of carboxylic acid.
7. Give the resonance structure of carboxylate anion.
8. Mention the inductive effect in monochloro acetic acid.
9. Write a note on esterification reaction with an example.
10. What happens when calcium salt of acetic acid is distilled.
11. Mention the uses of oxalic acid.
12. What is the action of dilute sulphuric acid with lactic acid ?
13. Give the structure of lactyl chloride and lactide.
319
(a)
(ii)
(iii)
COOH
|
COOH
glycerol
COOH
|
COOH
CH2 COOH
|
CH2COOH
383 K
NH3
NH3
320
322
323
Nitro propane
R
R
R
2o
3o
RCH2NO2
1o
CHNO2
C NO2
1-Nitro propane
1-Nitro-2-methyl propane
CH3
|
CH3 C CH2 NO2
|
CH3
1-Nitro-2,2-dimethyl propane
CH3
|
CH3 C CH3
|
NO2
324
Isomerism :
Besides chain and position isomerism Nitroalkene shows functional
isomerism.
Isomerism :
Nitro compounds exhibit the following three types of isomerism.
1. Chain isomerism arises due to the difference in the arrangement of
carbon atoms.
CH3 CH2 CH2 CH2 NO2
(linear chain)
1-nitro butane
(branched chain)
1-nitro-2-methyl propane
CH3 CH CH3
|
NO2
2-nitro propane
Methyl nitrite
CH3 N
CH2 = N
O
OH
Nitro
Acinitro
RX
+ AgNO2
CH3CH2Cl +
AgX + R NO2
AgNO2
methane
HONO2
+ HONO2
400oC
nitric acid
C6H13NO2
+ H2O
CH3NO2 +
H2O
nitro methane
20.1.2 Properties
Nitro alkanes are colourless pleasant smelling liquids. Nitromethane is
soluble in water, higher members are sparingly soluble in water but readily
soluble in organic solvents.
They are highly polar compounds. Hence they are high boiling than the
alkyl halides and alkanes. Nitro methane is slightly acidic.
O
+ O
+
H CH2 N
CH2 = N
(Nitrolic acid)
O
OH
(Nitroform)
(Tautomerism)
326
(Aci form)
CH2 = N
+
CH2 = N O
NaOH
+ H2O
O Na+
OH
This anion exhibits resonance.
O
CH2 = N
CH2 N
O
CH2 N
O
CH3CH2N
NaOH
Br
|
CH3 CH N
O
Br2
NaOH
O
Mono bromo
nitro ethane
Br
|
CH3 C N
|
Br
di bromo
nitro ethane
NaOH
HCHO + CH3NO2
dil. NaOH
CH2OHCH2NO2
2-nitro ethanol
CH3CHO + CH3NO2
dil. NaOH
CH3CHOHCH2NO2
1-nitro-2-propanol
CH3COCH3 + CH3NO2
dil. NaOH
(CH3)2COHCH2NO2
1-nitro-2-methyl-2-propanol
R NO2 +
6 [H]
RNH2
Sn/HCl
2H2O
CH3NH2
2H2O
Methylamine
(ii) Reduction under neutral conditions using Zn/NH 4Cl or Zn/CaCl2hydroxyl amines are formed.
RNO2
+ 4 (H)
Zn/NH4Cl
RNHOH
+ H2O
Hydroxyl amine
CH3 CH2NO2
Zn/NH4Cl
+ 4 [H]
(Nitro ethane)
CH3CH2NHOH
+ H2O
ethyl hydroxylamine
4. Hydrolysis :
When boiled with mineral acids primary nitro alkane, undergoes
disproportionation reaction to form carboxylic acid and hydroxylamine.
HCl
CH3CH2NO2 +
H2O
CH3COOH
acetic acid
328
NH2OH
hydroxylamine
CH3
|
CH3 C CH3
|
NO2
CH3NO2 + Cl2
NH2OH
329
CH3
NO2
p-nitro toluene
NO2
NO2
NO2
NO2
Nitrobenzene
CH3
O2N
m-dinitro benzene
2,4,6-trinitro toluene
There are some aromatic compounds which do not have nitro group
directly linked to the aromatic nucleus. The Nitro group is present in the
side chain.
CH3
|
CH2NO2
CHNO2
1-nitro,1-phenyl ethane
+ HNO3
Conc.
H2SO4
NO2
330K
H2O
NO2
NO2
H
330
NO2
H2SO4 + HONO2
HSO4
H
|
H O NO2
H2O
+ NO2
NO2
H
In the last step, the hydrogen atom attached to the carbon carrying the
nitro group is pulled out as a proton, by the Lewis base HSO4, so that
stable aromatic system is formed.
H
NO2 +
NO2
HSO4
H2SO4
6 [H]
Sn/con.HCl
or
Fe/con.HCl
C6H5NH2
2H2O
Aniline
C6H5NO2
4 [H]
Zn/NH4Cl
C6H5NHOH
+ H2O
Phenyl hydroxylamine
332
Na3AsO3/NaOH
C6H5 N = N C6H5
or glucose + NaOH
C6H5NO2
azoxy benzene
SnCl2 + NaOH
C6H5 N = N C6H5
azo benzene
Zn/NaOH
C6H5 NH NH C6H5
hydrazo benzene or
(N, N' - diphenyl hydrazine)
LiAlH4
C6H5NH2 [Aniline]
H2/Ni
Catalytic
hydrogenation
C6H5NH2
nitric acid and con. sulphuric acid and when the temperature is increased to
433 K nitro benzene gives 1,3,5-trinitro benzene.
NO2
NO2
Con.HNO3
Con. H2SO4/373 K
NO2
m-dinitrobenzene
NO2
NO2
Fuming HNO3
con.H2SO4/433 K
NO2
O2N
1,3,5-Trinitro benzene
2. Chlorination
Chlorine in presence of anhydrous ferric chloride generates positively
charged species. Chlorination takes place at meta position.
Cl
NO2
Cl2/FeCl3
NO2
3-chloro nitro benzene
NO2
con.H2SO4
SO3H
m-nitro benzene sulphonic acid
334
..
HNH
|
H
Ammonia
..
CH3 NH
|
H
Aliphatic amine
335
..
C6H5 N H
|
H
Aromatic amine
Amines are basic in nature. They accept protons forming alkyl or aryl
ammonium ions.
H+
..
+ RNH2
R NH2
|
Proton
Alkyl amine
C6H5NH2
ethylamine
aniline
R
|
R N H
Primary
Secondary
1o
Tertiary
2o
R
|
R N R
3o
>
2o amine
336
>
1o amine
IUPAC name
CH3 NH2
amino methane
methyl amine
CH3 CH CH3
|
NH2
2-amino propane
isopropyl amine
CH3CH2CH2NH2
1-amino propane
n-propyl amine
1-amino-2-methyl
propane
isobutyl amine
CH3
|
CH3 CH CH CH3
|
NH2
2-amino-3-methyl
butane
isopentyl amine
(N-methyl amino)
ethane
ethyl methyl
amine
CH3NH CH CH3
|
CH3
2-(N,N-dimethyl
amino) butane
337
Common name
dimethyl sec.butyl
amine
3H2/Ni or Pt
CH3CH2NH2
Nitro ethane
+ 2H2O
Ethylamine
(b)
(c)
CH3NO2
Sn (or) Zn/HCl
LiAlH4
CH3CH2 NH2
+ 2H2O
CH3NH2
Nitro methane
Methyl amine
4 [H]
Na/C2H5OH
(Acetamide)
CH3CH2NH2 + H2O
Ethylamine
LiAlH4
(b) CH3CONHCH3
CH3CH2NHCH3
(N-methyl acetamide)
(Secondary amine)
methylethylamine
3. Reduction of cyanides :
Primary amines can be prepared by reduction of alkyl cyanides (nitriles)
with H2/Ni or lithium aluminium hydride.
(a) CH3C N
(b) CH3C N
4 [H]
LiAlH4
Na/C2H5OH
CH3CH2NH2
CH3CH2NH2
Ether
(c) CH3C N
H2/Ni
CH3CH2NH2
338
CH3 N C
Methyl isocyanide
CH3 N C
CH3NHCH3
Dimethylamine
LiAlH4
CH3NH CH3
ether
5. From amides
By elimination reaction - primary amine is prepared.
Hoffmans hypobromite reaction or Hoffmans bromamide reaction
CH3CONH2
Br2/KOH
CH3NH2 +
CO2
CH3CO N Br + K+
..
..
..
..
..
CH3CO N Br
CH3 CO N
+ Br
Nitrene - an electron
deficient specie.
..
339
CH3NH2
CO2
methylamine
H2 O
methyl isocyanate
6. From ammonia :
By heating an alkyl halide with alcoholic ammonia in a sealed tube, a
mixture of primary, secondary, tertiary amines and quarternary ammonium
salt are obtained.
Nucleophilic substitution of alkyl halide or alcohol by Ammonolysis.
(Ammonia is the nucleophile in this reaction).
(a)
CH3Br + NH3
CH3NH2 + HBr
CH3Br + CH3NH2
(CH3)2 NH + HBr
CH3Br + (CH3)2 NH
(CH3)3 N + HBr
CH3Br + (CH3)3 N
(CH3)4 N+ Br
+ NH3
Al2O3
(CH3CH2) NH2
723K
1o
CH3CH2OH + (CH3CH2)2 NH
Al2O3
+ H2O
amine
(CH3CH2)2NH +
2oamine
diethyl amine
CH3CH2OH + (CH3CH2)2NH
Al2O3
(CH3CH2)3 N + H2O
3o amine
triethylamine
340
H2O
CO
NH
KOH
CO
CO
NK
RX
NR
CO
phthalimide
CO
N-alkyl phthalimide
potassium phthalimide
aqueous KOH
COOK
+ RNH2
alkylamine
COOK
potassium phthalate
>
Primary amine
341
>
Tertiary amine
342
2. Alkylation of amine :
When an amine is treated with alkyl halide, hydrogen atoms attached to
the nitrogen atom are successively replaced by alkyl groups. In the final
step, the tertiary amine adds one molecule of the alkyl halide to yield a
quaternary ammonium salt.
CH3NH2
CH3Br
1o amine
CH3NHCH3
CH3Br
(CH3)2 NCH3
2o amine
3o amine
CH3Br
(CH3)4 N+Br
Quarternary salts
Acetyl chloride
CH3NH2
CH3NHCOCH3
Methyl amine
N-methyl acetamide
CH3COOCOCH3
Acetic anhydride
Both the above reactions involve nucleophilic substitution reaction the nucleophile being alkyl amine and the leaving group the halide ion or
acetate ion.
4. Reaction with Nitrous acid :
(a) Primary amines react with nitrous acid to form alcohols and nitrogen
gas.
CH3NH2 + O = N OH
[CH3N=N OH]
primary amine
CH3OH + N2
unstable
(b) Secondary amines react with nitrous acid to form N-nitroso amines
which are water insoluble yellow oils.
(CH3)2 N H + HO N = O
(CH3)2 N N = O
Secondary amine
(c) Tertiary amines react with nitrous acid to form trialkyl ammonium
nitrite salts which are soluble in water.
(CH3)3 N
HONO
Tertiary amine
5. Carbylamine reaction :
Primary amines on heating with chloroform and alcoholic potash forms
a foul smelling substance called carbylamine or alkyl isocyanide.
CH3NH2 + CHCl3 + 3KOH
Chloroform
Methyl isocyanide
S=C=S
CH3 N = C = S
Carbondisulphide
methyl isothiocyanate
+ H2S
+ H2N CH3
C6H5CH = NCH3
Schiffs base
(benzal-N-methyl amine)
344
Secondary amine
R2NH
Tertiary amine
R3N
forms N-nitroso
amine.
forms salt.
2. With CHCl3/KOH
forms carbylamine
No reaction.
No reaction
form N,N-dialkyl
acetamide.
No reaction
No reaction
No reaction
Forms N,N-dialkyl
oxamic ester, a liquid.
CONR2
|
COOC2H5
No reaction
COOC2H5
CONHR
|
2RNH2 |
CONHR
COOC2H5
dialkyl oxamide, a
solid at room
temperature is
formed.
6. With three molar
proportion of alkyl
halide, quarternary
ammonium saltcrystalline
compound
is formed.
3RX + RNH 2
R4N+X
R2NH + 2RH
R4N+ X
R3N + RX
R4N+ X
NH2
(ii) Amines in which the amino group is attached to the side chain of
benzene ring.
CH NH
2
benzyl amine
Aralkyl amines :
These are amines having aromatic system such as benzene ring but the
amino group is present in the side chain.
CH2NH2
CH2NH2
H3C
Benzyl amine
H2/Ni
C6H5CH2NH2
Benzonitrile
LiAlH4
H2/Pd
C6H5CONH2
C6H5CH2NH2
Benzamide
LiAlH4
346
2. From benzylbromide
By the action of alcoholic ammonia on benzyl bromide.
C6H5CH2 Br
+ HNH2
C6H5CH2NH2 + HBr
benzylamine
2. Substitution at Nitrogen
N-alkylation : With alkyl halide it forms secondary amine, tertiary amine
and finally quaternary ammonium salt.
C6H5CH2NH2
CH3Br
C6H5CH2NHCH3
+
CH3Br
C6H5CH2 N (CH3)3 Br
C6H5CH2 N (CH3)2
CH3Br
N-Acetylation :
With acetyl chloride or heating with acetic anhydride N-benzyl acetamide
is formed.
C6H5CH2 NH2 +
ClCOCH3
C6H5CH2NHCOCH3 + HCl
N-benzyl acetamide
C6H5CH2NHCOCH3 + CH3COOH
N-benzyl acetamide
C6H5CH2OH
+ N2
4. Oxidation
On oxidation with permanganate the side chain with the amino group is
oxidised to give benzoic acid.
CH2NH2
KMnO4
COOH
[O]
Benzylamine
Benzoic acid
NH2
CH3
o-Toluidine
Aniline
H2/Cu/SiO2
NH2
543 K
NH2
Sn/HCl
(H)
348
2H2O
Reduction with Fe/con. HCl is used for the large scale preparation of
aniline.
3. By the ammonolysis of chloro benzene at high temperature and
pressure in presence of copper salts, aniline is prepared.
C6H5Cl + 2NH3
CuCl2
C6H5NH2 + NH4Cl
ammonium chloride
C6H5CONH2
KOH
C6H5NH2
+ CO2
20.4.5 Properties
A colourless oily liquid sparingly soluble in water. Soluble in organic
solvent. It has higher boiling point than benzene, because of intermolecular
hydrogen bonding. This liquid turns brown on exposure to air due to
oxidation.
Basic nature of Aromatic amines :
Aniline is less basic than aliphatic amines. This is because, the lone pair
of electrons on the nitrogen atom is involved in resonance and is not easily
available for donation to protons. Because of positive charge on nitrogen
protonation becomes difficult.
H2N:
H2N+
H2N+
H2N+
()
()
()
3. Ortho and para positions are more electron dense hence electrophilic
substitution takes place at ortho and para positions.
4. Nitrogen is strongly bound to the nucleus hence is not easily removed.
(partial C-N double bond character)
1. Basic property :
These form crystalline salts with strong mineral acids such as HCl or
H2SO4.
C6H5NH2
C6H5NH3 Cl
+ HCl
2. Substitution of nitrogen :
(a) Alkylation with alkyl halides it forms 2o, 3o amines and finally
quaternary ammonium salt.
C6H5NH2 + CH3I
C6H5N (CH3)2
C6H5NHCH3
CH3I
C6H5N (CH3)2
2o amine
3o amine
(N-methyl aniline) (N, N-dimethyl aniline)
+
CH3I
C6H5N (CH3)3 I
Phenyl trimethyl ammonium iodide
(b) Aniline reacts with acetyl chloride and acetic anhydride to form
corresponding amides called anilides.
C6H5NH2
+ ClCOCH3
C6H5NHCOCH3 + HCl
Acetyl chloride
N-phenyl acetamide
C6H5NH2 + CH3COOCOCH3
C6H5NHCOCH3 + CH3COOH
Acetic anhydride
Acetanilide
+ ClCOC6H5
NaOH
benzoyl chloride
C6H5NHCOC6H5
benzanilide
+ O = CHR
C6H5N = CHR
(Aldimine or Schiffs base)
In all the above reactions the initial stage is the nucleophilic attack.
The nucleophile is the amine and the site of attack is either halogen carrying
carbon or carbonyl carbon. This is an addition - elimination reaction.
4. Reaction with nitrous acid :
3. A cold solution of sodium nitrite reacts with aniline dissolved in
hydrochloric acid, a clear solution is obtained. This solution contains
benzene diazonium chloride. This reaction is known as diazotisation.
HCl
C6H5N H2 + O=NOH
C6H5 N = N Cl
(Benzene diazonium chloride)
5. Carbylamine reaction :
Aniline reacts with chloroform and alcoholic KOH to give an offensive
smelling liquid, phenyl isocyanide.
C6H5NH2 + CHCl3 + 3KOH
C6H5NC
+ 3KCl
+ 3H2O
(phenyl isocyanide)
6. Oxidation :
Aromatic amines are readily oxidised by dichromate and sulphuric acid
to p-benzoquinone.
NH2
O
K2Cr2O7/H+
351
COCl2
C6H5NH
C=O + 2HCl
Carbonyl chloride
C6H5NH
S-diphenyl urea
CS2
C6H5NH
C=S + H 2 S
carbondi
sulphide
C6H5NH
S-diphenyl
thiourea
NH2
+ 3Br2 /H2O
Br
Br
+ 3HBr
Br
2,4,6-nitro bromoaniline
352
(b) Sulphonation :
Heating with fuming sulphuric acid, p-amino benzene sulphonic acid is
formed.
NH2
NH
2
H2SO4
353K
H2O
SO3H
NH2
NH3+
NH3
HNO3
H2SO4
NH2
NO2+
NaOH
(HNO3 + H 2SO4)
NO2
NO2
(m-nitroaniline)
NHCOCH3
NH2
CH3COCl
NH2
H3O+
HNO3/H2SO4
NO
2
20.4.6 Uses of aniline
1. For preparing dyes and dye intermediates.
+ CH3COOH
NO2
SUMMARY
AMINO COMPOUNDS
Structure, nomenclature, classification and isomerism including
metamerism - of aliphatic amines.
Preparation - Reduction of nitro compounds, amides, cyanides phthalimide synthesis - nucleophilic substitution - Ammonolysis.
Properties - hydrogen bonding and polar - higher boiling points - basic
and nucleophilic character.
Classification - primary, secondary and tertiary amine - Basic strength
of amines - N-alkylation, N-acylation, carbylamine reaction - quaternary
ammonium salt.
Uses - Distinction between primary, secondary and tertiary amines.
Aralkyl amine - Benzyl amine - preparation - reduction of amides,
cyanides - properties. Weaker a base than aliphatic amines - gives reactions
of aliphatic primary amine - oxidation of side chain to give benzoic acid.
Aromatic amines - aniline and toluidines - structure, nomenclature and
isomerism - preparation - reduction of nitro benzene - chemical and catalytic
- chloro benzene and ammonia, Hoffmann reaction.
Properties - inter molecular hydrogen bonding - higher boiling point less basic than aliphatic amines - resonance in aniline - N-alkylation, Nacylation, formation of Schiffs base, carbylamine reaction, reaction with
phosgene, carbondisulphide - Formation of phenol - diazotisation and
formation of azo dyes - electrophilic substitution in the benzene ring bromination, sulphonation and nitration - uses.
20.5 ALIPHATIC NITRILES
Alkyl cyanides :
These are compounds in which one hydrogen atom is replaced from a
hydrocarbon by a cyanide group.
HCN
R CN
354
RH
CH3COOH
Acetic acid
C6H5COOH
Benzoic acid
As cyanide
HCN
Hydrogen cyanide
CH3CN
Methyl cyanide
Acetonitrile
Ethane nitrile
CH3CH2CN
Ethyl cyanide
Propionitrile
(or)
propiononitrile
Propane nitrile
isopropyl
cyanide
isobutyronitrile
2-methyl-propane
nitrile
(or)
2-cyano propane
(as a substituent)
CH3CHCH3
|
CN
As acid nitrile
Formonitrile
355
IUPAC name
Methane nitrile
..
[ Ar N N :
Ar N = N : ] X
N+=N
N+N
N+N
(+)
(+)
356
HNO2 + NaCl
273 278 K
C6H5N2+Cl + 2H2O
This is stable only under ice cold condition. In the dry condition it is
quite unstable and decomposes violently.
20.6.2 Properties
Colourless crystalline solids turning brown on exposure to air. Only
diazonium [ArN2+ BF4] fluro borate can be dried without decomposition,
soluble in water and alcohol and insoluble in ether.
Chemical properties :
They are highly reactive compounds. They undergo reaction in which
(1) N2 group is retained or (2) eliminated. In both cases useful compounds
can be prepared. They are as useful as Grignard reagent for synthesis.
1. Reactions in which N2+ X is replaced.
(a) Reduction to arenes :
Benzene diazonium chloride with Hypophosphorous acid, is reduced to
benzene.
C6H5 N2 Cl
H
H
H3PO2
Cu+
C6H6 + N2 + HCl
C6H5 N2 Cl
HO
C6H5OH + N2 + HCl
C6H5OCH3
Aromatic ethers
(anisole)
C6H5 N2 Cl
C6H5OCOCH3
CH3COO
+ N2 +
HCl
+ N2 + HCl
Phenyl acetate
(ester)
C6H5N2Cl
C6H5NO2
Cu+
C6H5N2Cl
HCl
C6H5 Cl
N2
Cu2Cl2
C6H5N2Cl
HBr
Cu2Br2
C6H5Br
+ N2
C6H5N2Cl
Cu
HCl
Cu
HBr
C6H5Cl + N2
C6H5Br + N2
Cu2(CN)2
C6H5CN
+ N2 + HCl
+ KCN
Cu
C6H5CN
+ N2
+ KCl
C6H5N2Cl
+ C6H6
NaOH
C6H5 C6H5
Biphenyl
+ N2
+ HCl
C6H5N2Cl
C6H5NHNH2
+ HCl
C6H5N = N
OH
OH
The aromatic compound with which it couples should have any one of
the groups like OH, NH2, OR, NHR, NR2 etc. coupling usually occurs
at para position.
ALL THE COUPLING REACTIONS INVOLVE
I. Formation of diazonium ion C6H5N2+ (an electrophile)
II. Electrophilic substitution on electron rich aromatic compounds like
phenols, amines etc., at para-position.
360
C6H5N2+ +
C6H5N2
+
OH
OH
H
+
OH
C6H5N=N
N2Cl +
OH
N(CH3)2
+ H+
N=N
N, N - dimethyl aniline
N(CH3)2
N=NNH
Diazoaminobenzene
(Substitution at Nitrogen)
(II)
N=NNH
HCl
[Rearrangement]
N=N
NH2
SUMMARY
Benzene Diazonium chloride - structure - diazotisation of aniline properties - stable at low temperature - hydrogenolysis to benzene, hydrolysis
to phenol, formation of halo benzene, cyano benzene, nitrobenzene, anisole
- reduction to phenyl hydrazine - diazo coupling with aromatic amines and
phenols - formation of dyes.
Name reactions
1. Sandmeyer reaction
2. Gattermann reaction
3. Gomberg reaction
4. Diazo coupling reaction
Alkyl cyanides - nomenclature as Nitriles.
SELF EVALUATION
(A) Choose the correct answer :
(b) C2H5ONO
(d) C2H5NC
O
(a) position
(b) chain
(c) functional
(d) tautomerism
3. In nitro alkanes NO2 group is converted to NH2 group by the reaction
with
(a) Sn/HCl
(b) Zn dust
(c) Zn/NH4Cl (d) Zn/NaOH
4. When nitromethane is reduced with Zn dust + NH4Cl in neutral medium,
we get
(a) CH3NH2
(b) C2H5NH2 (c) CH3NHOH (d) C2H5COOH
5. The compound that is most reactive towards electrophilic nitration is
(a) Toluene
(b) benzene
(c) benzoic acid (d) nitrobenzene
6. Nitromethane condenses with acetaldehyde to give
(a) nitro propane
(b) 1-nitro-2-propanol
(c) 2-nitro-1-propanol
(d) 3-nitro propanol
7. Which of the following compounds has the smell of bitter almonds ?
(a) aniline
(b) nitro methane
(c) benzene sulphonic acid
(d) nitrobenzene
362
CH3 CH CH3
|
NH2
NaNO2/HCl
(a) C6H5Cl
(c) C6H5N2Cl
X. Identify X.
(b) C6H5NHOH
(d) C6H5OH
363
Ans : Aniline
CuCN
LiAlH4
Benzene
cyano benzene
HCl, 0oC
diazonium chloride
Benzyl amine
23. What are the reagents that would convert the following into Ethyl amines ?
(a) CH3CONH2 (b) CH3CN (c) CH3CH2NO2 (d) CH3CH = NOH
24. Account for the following :
(a) (CH3)2NH is a stronger base than NH3
(b) CH3CH2NH2 is more basic than CH3CONH2
(c) Aniline is less basic than Ethyl amine
(d) On sulphonation of aniline, p-amino benzene sulphonic acid is formed.
25. What is the action of NaNO2/HCl (aq) at ice cold temperature on
(a) C2H5NH2 (b) C6H5NH2 (c) (CH3)2NH (d) (CH3)3N
26. What happens when ethylamine is treated with
(a) CHCl3/NaOH (b) CS2 (c) COCl2 (d) C6H5CHO
27. Justify :
(a) Diazo coupling reaction is an example of aromatic electrophilic
substitution reaction
(b) Formation of acetanilide from aniline and acetic anhydride is a
nucleophilic attack by aniline
(c) Formation of methylamine by ammonolysis of methyl iodide is an
example of SN2 reaction
(d) Addition of bromine water to aniline, gives a white precipitate.
This is an example of aromatic electrophilic substitution.
28. What is the action of
(a) Diethyl oxalate on Ethylamine
(b) Diethyl oxalate on Diethyl amine
(c) Nitrous acid on Diethyl amine
(d) Nitrous acid on Triethyl amine
365
azoxy benzene
(c) Nitrobenzene
Hydrazobenzene
C6H6
(b) C6H5NO2
C6H5OH
368
(c) C6H5NH2
(d) C6H5NH2
C6H5I
C6H5NO2
C6H5I + KCl
C6H5N=NC6H4OH
C6H5OCH3
C6H5OH
KEY
1.
(d)
2.
HNO2
(a) C6H5NH2
(a) C6H5NH2
C6H5NH2
HNO2
HNO2
C6H5N2Cl
HCl
C6H5NH2
HCl
C6H5N2Cl
HNO2
HCl
HNO2
HCl
C6H5N2Cl
369
C6H6
C6H5N2Cl
KI
C6H5N2Cl
H3PO2
H2O
C6H5I
NaNO2
HCl
Cu2Cl2
C6H5NO2
C6H5Cl
C6H5OH
(b) C6H5NH2
(c) C6H5NH2
HNO2
HCl
HNO2
HCl
3.
C6H5NO2
C6H5Cl
Sn/HCl
NH3
C5H5N2Cl
C6H5N2Cl
C6H5N2Cl
HNO2
HCl
4. (a)
(b)
(c)
(d)
C6H5N=N C6H4NH2
CH3OH
Sn/HCl
C6H5CN
H3O+
C6H5OCH3
C6H5NHNH2
C6H5COOH
Cu2(CN)2
HBr
Cu2Br2
I
C6H5N2+
CH3OH
H2O
C6H5CN
C6H5N2Cl
KCN
C6H5N2Cl
C6H5N = NC6H4OH
C6H5N2Cl
HCl
HCl
C6H5N2Cl
Aniline
HNO2
C6H5NH2
C6H5NH2
HNO2
KCN
Cu2(CN)2
HCl
C6H5NH2
Phenol
C6H5Br
Na
C2H5Br
C6H5C2H5
dry ether
- nucleophile
- electrophile
- nucleophile
- nucleophile
REFERENCES :
1. Organic reactions, Conversions, Mechanism & Problems. - R.D. Madan,
S.Chand & Co. Ltd.
2. A guide book to Mechanism in organic chemistry. - Peters Sykes Pearson Education Ltd.
_______
370
21. BIOMOLECULES
LEARNING OBJECTIVES
@ Recognises the importance of carbohydrates, proteins, amino acids and
lipids.
@ Classification of carbohydrates.
@ Structural elucidation of simple carbohydrates.
@ Proteins and amino acids.
@ Classification, structure and functions of lipids in biosystems.
A living organism is a collection of organic molecules which interact
with each other and with their environment in a very unique way. All living
organisms are made of one or more cells which are considered as the smallest
units of life. Cells are essentially packets of chemicals necessary for life. The
compounds present in cells are composed of carbon, hydrogen, oxygen,
nitrogen, phosphorus and sulphur. Nearly all the carbon compounds found
in living cells can be placed into one or another of the following four classes.
(i) Carbohydrates, (ii) Amino acids and proteins, (iii) Nucleic acids and
(iv) Lipids.
21.1 CARBOHYDRATES
Carbohydrates are polyhydroxy aldehydes or polyhydroxy ketones. They
are naturally occuring organic substances. They are present in both plants
and animals. Carbohydrates are formed in the plants by photosynthesis from
carbon dioxide and water in sunlight.
Classification :
O
||
( CH)
O
||
( C )
The aldoses and ketoses are further divided into sub-groups on the basis
of the number of carbon atoms in their molecules, as trioses, tetroses,
pentoses, hexoses etc.
Thus monosaccharides are generally referred to as aldotrioses,
aldotetroses, aldopentoses, aldohexoses, ketohexoses etc.
The aldoses and ketoses may be represented by the following general
formulae.
H
C=O
|
(CHOH)n
|
CH2OH
aldoses
(n = 1, 2, 3, 4, 5)
CH2OH
|
C=O
|
(CHOH)n
|
CH2OH
ketoses
(n = 0, 1, 2, 3, 4)
(ii) Oligosaccharides :
+ H2O
C6H12O6
Sucrose
+ C6H12O6
Glucose
Fructose
Raffinose
Galactose
Glucose
Fructose
+ n H2O
H+
Starch
n C6H12O6
Glucose
Non-sugars
(Polysaccharides)
Monosaccharides oligosaccharides
Aldoses
Homopolysaccharides
Heteropolysaccharides
Ketoses
Disaccharides
...
...
+ H2O
H+
Cane sugar
C6H12O6 +
C6H12O6
Glucose
Fructose
Structure of Glucose :
The structure of glucose has been derived from the following facts.
1. Elemental analysis and molecular weight determination show that the
molecular formula of glucose is C6H12O6.
2. Complete reduction of glucose with concentrated hydriodic acid in the
presence of red phosphorous produces n-hexane as the major product.
This indicates that the six carbon atoms in the glucose molecule form an
unbranched chain of six carbon atoms.
Glucose
HI/P
Reduction
C
OH )
group.
4. Glucose reacts with hydroxylamine to form a monoxime or adds only
one mole of HCN to give a cyanohydrin. This reaction indicates the
O
||
presence of either an aldehyde
or a ketone
( CH)
O
||
( C ) group.
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5. Mild oxidation of glucose with bromine water gives gluconic acid. This
indicates the presence of an aldehyde group since only the aldehyde
group can be oxidised to an acid, containing same number of carbon
atoms. Since the six carbon atoms in glucose form a consecutive
unbranched chain, the aldehyde group, must occupy one end of this chain.
6. Further oxidation of gluconic acid with nitric acid gives saccharic acid.
This indicates the presence of a primary alcoholic group.
Glucose
COOH
|
(CHO)4
|
CH2OH
Br2/H2O
Mild
oxidation
HNO3
Strong
oxidation
gluconic acid
COOH
|
(CHOH)4
|
COOH
saccharic acid
O
*
*
*
*
C
|
CHOH
|
CHOH
|
CHOH
|
CHOH
|
CH2OH
Glucose
(2,3,4,5,6 penta hydroxy hexanal)
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FRUCTOSE :
Fructose is present in abundance in fruits and hence it is called as fruit
sugar. It is also present in cane sugar and honey alongwith glucose in
combined form. Since naturally occuring fructose is laevorotatory, it is also
known as laevolose. It is a ketohexose.
Preparation :
+ H2O
dil.H2SO4
Cane sugar
C6H12O6
Glucose
+ C6H12O6
Fructose
The structure of fructose has been derived from the following facts.
1. Elemental analysis and molecular weight determination show that the
molecular formula of fructose is C6H12O6.
2. Complete reduction of fructose with concentrated hydriodic acid in the
presence of red phosphorous gives n-hexane as the major product. This
indicates that the six carbon atoms in the fructose molecule form a
consecutive unbranched chain.
Fructose
HI/P
Reduction
Fructose
CH2OH
|
CN Hydrolysis
C
|
OH
(CHOH)3
|
CH2OH
CH2OH
| COOH
C
| OH
(CHOH)3
|
CH2OH
Reduction
CH3
| COOH
C
| H
(CH2)3
|
CH3
2-methyl hexanoic acid
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fructose
(1, 3, 4, 5, 6, pentahydroxy-2-hexanone)
21.3 DISACCHARIDES
Disaccharides are sweet tasting, crystalline, water-soluble substances,
easily hydrolysed by enzymes and dilute mineral acids to two monosaccharide
units.
C12H22O11 + H2O
C6H12O6 +
disaccharide
monosaccharide
C6H12O6
monosaccharide
HC
|
H C OH
|
HO C H
|
H C OH
|
HC
|
CH2OH
O
O
CH2OH
|
C
|
HO C H
|
H C OH
|
HC
|
CH2OH
Polysaccharides
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(C6H10O5)n
Starch
C12H22O11
Dextrin
Maltose
C6H12O6
Glucose
nC12H22O11
Maltose
Starch solution gives a blue colour with a drop of iodine. The exact
chemical nature of starch varies from source to source. Even the starch
obtained from same source consists of two fractions (i) amylose and
(ii) amylopectin.
Cellulose : Cellulose is found in all plants and so is the most abundant
of all carbohydrates. It is the material used to form cell walls and other
structural features of the plants.
Cellulose is insoluble in water and in most of the organic solvents. When
it is boiled with dilute H2SO4, it is completely hydrolysed into D-glucose.
(C6H10O5)n
Cellulose
nH2O
nC6H12O6
Glucose
H O
|
||
R C C OH
|
NH2
-carbon
NH2
|
R CH COOH
|
R CH COO
Amino acid
Zwitter ion
H+
H O
| ||
H+3NCCO OH
|
R
Zwitter ion
(I)
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H O
| ||
H2NCCO
|
R
High pH Anion
(Basic solution) (III)
Carboxyl group
of one amino acid
C N + H2O
|| |
O H
H N
|
H
Amine group of
other amino acid
Peptide bond
Alanine
Glycylalanine (a dipeptide)
CH3
|
(ii) H2N CH COOH + H2NCH2COOH
Alanine
CH3
|
H2NCH2CONHCHCOOH
Glycine
CH3
|
H2NCHCONHCH2COOH
Alanyl glycine (a dipeptide)
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21.5 LIPIDS
Lipids form a group of organic compounds which are widely distributed
in living system. Lipids are mainly divided into three types, namely simple,
compound and derived, depending on the basis of the nature of products
obtained on hydrolysis.
Functions of lipids in biosystems :
Fats and oils act as storage of energy in plants and animals. In the animal
body, fats are stored in fatty tissues, which are almost pure fat,. Fat give
about 2 times as much energy as carbohydrates or proteins. Thus, as far as
weight is concerned, storage of fat is the most economical way for the body
to maintain a reserve energy supply. Fat is a poor conductor of heat. Hence,
fat layer under skin serves to prevent losses of heat from the body.
Wax acts as a protective agent on the surfaces of animals and plants.
Waxy coating on the surface of plants and fruits protects them from excessive
loss of moisture and becoming infected with fungi and bacteria.
Phospholipids like lecithins, and cephalins play a greater role in biosystem.
The lecithins are required for normal transport and utilisation of other lipids,
especially in the liver. lecithin aids in the organisation of the cell structure.
Cephalins are found in the brain. Cephalins have been implicated in the
process of blood coagulation.
Galactolipids occur in considerable amount in the white matter of the
brain and of all nervous tissue. The presence of galactose in the glycolipids
suggests the importance of milk sugar in the diet of infants and children
during the development of the brain and nervous system.
383
SELF EVALUATION
(A) Choose the correct answer :
1.
2.
3.
4.
5.
386
SUMMARY :
The molecules, which form the basis of our life, are complex molecules
called biomolecules which in turn combine and form the living beings,
carbohydrates, proteins, nucleic acids and lipids are biomolecules.
Carbohydrates are polyhydroxy aldehydes or polyhydroxy ketones. They
are naturally occuring organic substances.
Proteins are complex polyamides formed from amino acids. They are
essential for proper growth and maintenance of body. They contain many
peptide CONH bonds. Therefore, proteins are long polymers of amino
acids linked by peptide bonds.
Amino acids are the compounds which contain carboxylic acid group
and amino group. Amino acids form proteins. Except glycine all the -amino
acids are optically active. The dipolar form of aminoacid is called Zwitter
ion. The pH at which the amino acid shows no tendency to migrate when
placed in an electric field is known as isolectric point.
REFERENCES :
1. Organic Chemistry by Morrison and Boyd.
2. Chemistry of natural products by O.P. Agarwal Vol. I and II.
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387
The effects of the drugs belonging to the first category are described by
the term chemotherapy.
Treatment of certain diseases by destroying the invading organism
without damaging the cells of the host, by the use of certain organic
compounds in known as chemotherapy.
1. Anaesthetics
The drugs which produce loss of sensation are called anaesthetics. They
are classified into two types. (i) General anaesthetics are the agent, which
bring about loss of all modalities of sensation, particularly pain along with
reversible loss of conciousness. (ii) Local anaesthetics prevent the pain
sensation in localised areas without affecting the degree of conciousness.
(i) Nitrous oxide N2O : It is a colourless, inoragnic non-irritating gas.
It is the safest of the anaesthetic agents. This is used after mixing general
anaesthetics like ether.
(ii) Chloroform CHCl3 : Volatile liquid. It has pleasent smell and sweet
taste. With oxygen it forms a toxic carbonyl chloride. Hence it is not used
now.
(iii) Ether : The present form of C2H5OC2H5 is a volatile liquid. This
is mixed with stabilizer 0.002% propyl halide. After absorption by tissues it
attacks the central nervous system and makes unconcious.
2. Analgesics
Analgesics are the compounds which relieve all sorts of pains without
the loss of consciousness. These are also called as pain killer, or pain
relievers. These are effective in headaches, myalgia and arthalgia.
Examples : Aspirin, Novalgin are commonly used analgesics. Aspirin
acts both as antipyretic as well as analgesic. Certain narcotics (which produce
sleep and unconsciousness) are also used as analgesics.
3. Antipyretics
Antipyretics are the compounds which are used for the purpose of
reducing fever (lowering the body temperature to the normal). The most
389
OC2H5
OH
NHCOCH3
NHCOCH3
COOH
phenacetin
p-acetamidophenol
(paracetamol)
4. Antiseptic :
Antiseptic is a substance that rendors micro organisms innocuous by
killing them or preventing their growth. This term is used particularly for
preparations applied to living tissues.
(i) Iodoform, CHI3 is used as an antiseptic and its 1% solution is a
disinfectant.
(ii) 0.2 percent solution of phenol acts as an antiseptic and its 1% solution
is a disinfectant.
5. Antiprotozoals (Antimalarial)
Malaria causes shivering and fever. The body temperature rises to 103It causes physical weakness with the side-effects in lever and also
causes aneamia.
106oF.
Extracts of certain plants, specially the roots and stems, are extensively
used as antimalarial. Cinchona bark which gives rise to quinine acts as
antimalarial. The last antimalarial discovered in 1961 is pyrimethamine.
However, quinine, primaquine and chloroquine are some of the best
antimalarials.
Chloroquine is used specially to control malarial parasite of the ovale
vivax etc. It is not used in curing the disease. It is used as a mixture with
other antimalarials.
390
6. Antibiotics
Many microorganisms (bacteria, fungi and moulds) produce certain
chemicals which inhibit the growth or metabolism of some other
microorganism. Such chemical compounds are known as antibiotics. These
need be present only in low concentration to be effective in their antibiotic
action. The first antibiotic, discovered by Alexander Fleming in1929, from
mould Penicillium notatum, was penicillin.
There are three main sources of antibiotics.
(i) Bacteria (ii) Fungi
Penicillins
Penicillins is the name given to the mixture of natural compounds having
the molecular formula C9H11N2O4 S - R, and differing only in the nature of
R. Depending upon the nature of R, there are at least six natural penicillins.
Uses. Penicillin is extensively used for rheumatic fever, narrowing of
heart wall, bronchitis, and pneumonia etc.
7. Antacids
Quite often, after eating oily and spicy food, one may feel uncomfortable
due to some burning sensation in stomach/food pipe. This is due to the
imbalance in the acidity in the stomach.
Certain drug formulations provide relief from such burning sensation.
These are known as antacids.
Antacids are available in tablet as well as gel/syrup forms. These antacids
contain magnesium and aluminium hydroxides, in addition to flavouring
agents and colour.
8. Antispasmodics
There are a group of medicines that include natural bellodona alkaloids
(atropine, bellodona).
391
|
N=NO
Azoxy
Carbonyl
>C=O
Polyene
(HC=CH)n
O
Azo
N = N
Quininoid
OH
(a) azobenzene,
N=N
is the chromogen
N=N
is the chromophore
OH
is auxochrome
393
nCH2 = CH2
ethene
( CH2 CH2 )n
high pressure
polyethene
( CH2 CH )n
|
C6H5
styrene
polystyrene
Na
acrylonitrile
adipic acid
H
H O
O
|
| ||
||
N(CH2)6NC(CH2)4C n
nylon-66
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SELF EVALUATION
(A) Choose the correct answer :
1. The substance capable of absorbing blue light from the visible radiation
would appear
(a) yellow
(b) yellow-green
(c) red
(d) blue
2. The unsaturated group(s) present in an organic compound is/are called
(a) chromogens
(b) auxochromes
(c) no specific name
(d) chromophores
3. If an auxochrome does not affect the colour of the chromogen, it should
be present in the ................ position relative to chromophore.
(a) para(b) meta(c) ortho- (d) same4. In the compound, O2NC6H4N=NC6H4N(CH3)2, the chromophore
is
(a) NO2 (b) N = N (c) NO2 and N = N (d) N (CH3)2
5. Diazonium salts give coupling reactions with
(a) alcohol (b) aromatic amines (c) all amines (d) amines and phenols
6. Substances which bring the body temperature down to normal
temperature are known as
(a) antipyretics (b) analgesics
(c) antibiotics
(d) none
7. The compound which acts both as antipyretic as well as analgesic is
(a) phenacetin (b) sulpha drugs (c) paracetamol
(d) aspirin
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8. A 1% solution of phenol is a
(a) antiseptic (b) disinfectant (c) antimalarial drug (d) antihistamine
9. The medicine used for curing rabies is called
(a) antibacterial (b) antiviral
(c) antifungal
(d) antibiotics
10. The substance that function as a moisture barrier between the skin and
the atmosphere is called
(a) preservative (b) emulsifier (c) anticaking agent (d) moisturizer
(B) Answer in one or two sentences :
1. Define chemotherapy.
2. What are anaesthetics ? Give one example.
3. In what way antipyretics are important.
4. Why Iodoform and phenolic solutions are called antiseptic ?
5. Give two examples of antimalarials.
6. What are antibiotics ?
7. In what way antacids are important ?
8. What are antipasmodics ?
9. Give any two characteristics of Dye.
10. What are chromophores ? Give two examples.
11. What are artificial sweetening agents ? Give two examples.
12. What is Buna-S ?
(C) Answer not exceeding sixty words :
1. Write briefly on antibiotics ? In what way antipasmodics are helpful ?
2. Explain briefly on characteristics of rocket propellants.
SUMMARY :
The chemicals which can cure several diseases are called drugs. Medicinal
chemistry deals with action of various chemical compounds which are used
as drug. Each drug is unique in character. Anaesthetics, analgesics,
antipyretics, antimalarials, antacids, antispasmodics are very important. The
nature of dyes and the relation between colour and structure of dyes.
Chemicals used in food, are also dealt with. Rocket propellants are discussed
briefly. A detailed account on polymers like, addition, condensation polymers,
discussed.
REFERENCES :
1. Biochemistry by Leninger.
2. Pharmaceutical Chemistry by Ghosh.
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399