Preparation and Properties of Compounds

Page No.
-1
Preparation & Properties of Compounds
BORON FAMILY
Elements : B, Al, Ga, In, Tl
General eletroni onfiguration :
2 1
ns , np
!elting Points, Boiling Points and strutures
The melting points of group III elements do not show a regular trend as did the metals of group I
and II, because B and Ga have unusual crystal structures.
Boron has an unusual crystal structure which results in the melting point being very high. Other
elements form metallic bonding, but small sie and high lonisation energy ma!e this impossible
for boron. Boron e"ists in four different allotropic forms, all of which contains icosahedral units
with boron atoms at all 12 corners. #Icosahedral contains 12 corners and 2$ faces%. Only &'( of
the space is occupied by the atoms, compared with ')( for a close*pac!ed arrangement. This
shows that icosahedra fill up space ineffectively.
The elements +l, In and TI all have close*pac!ed metal structures Ga has an unusual structure.
,ach metal atom has one close neighbour at a distance of 2.)& - and si" more distant neighbours
at distance between 2.' - and 2.'. -. This remar!able structure tends towards discrete diatomic
molecules rather than a metallic structure. This accounts for the incredibly low melting point of
gallium at &$/0
!elting Point "#C$ Boiling Point "#C$
B
+l
Ga
In
Tl
211$
22$
&$
13'
&$&
&23$
2)2'
2)$&
2$1$
1)3'
+s is obvious from the above table, the melting point decreases in the group but irregularities
occur. B has very high melting point because of its uni4ue covalent structure. Ga has e"tremely
low melting point again because of its uni4ue structure.
The boiling point for B is unusually high, but the values for Ga, In and Tl decrease on
descending the group as e"pected. 5ote that the boiling point for Ga is in line with the others,
whereas its melting point is not. The very low melting point is due to the unusual crystal
structure, but the structure no longer e"its in the li4uid.
%i&e of atoms and ions
The metallic radii of the atoms do not increase regularly on descending the group. 6owever, the
values are not strictly comparable because of their uni4ue structures.
7etallic radius
#-%
Ionic radius
( )
&
7 -
+
( )
7 -
+
8aulings
electronegativity
B
+l
Ga
In
Tl
#$.113%
1.)&
#1.223%
1.2'
1.'$
#$.2'%
$.3&3
$.22$
$.1$$
$.113
9
9
1.2
1.)
1.3
2
1.3
1.2
1.'
1.1
The ionic radii for
&
7
+
increase down the group, though not in the regular way as observed in
Group I and II. There are two reasons for this.
NA'A(ANA )*A'+A CENT'E
,-1-A, )imension )urga To.er, Plot No. / 1-, %etor 0 !ar1et, ).ar1a Ne. )el2i / 11--34, P2 : 045,13,0 6 ,4
Page No.-,
#i% There is no evidence for the e"istence of
&
B
+
under normal condition and the value of
ionic radius is an estimate.
#ii% The electronic structures of the elements are different Ga and In have a
1$
d
inner shell
which is poorly screening and so have higher ionisation energies than would otherwise be
e"pected. This contraction in sie is sometimes called the d*bloc! contraction.
In a similar way Tl follows immediately after 1) f*bloc! elements.. The sie and
ionisation energy of TI are affected even more by the presence of 1) f*electrons, which
shield the nuclear charge even less effectively. The contraction in sie from these f*bloc!
elements is called the lanthanide contraction.
Eletropositi7e C2arater
The electropositive or metallic nature of the elements increase from B to +l, but then
decreases from +l to TI as is shown by the standard electrode potentials for the reaction:
&
7 &e 7
+
+
( )
&
7 ; 7 <olts
+
( )
1
7 ; 7 <olts
+
B
+l
Ga
In
Tl
#9$.1'%=
91.22
9$.32
9$.&)
>1.22
$.33
9$.'.
f
9$.11
9$.&)
& & 2
=?or 6 BO &6 &e B &6 O
+
+ + +
f
<alue in acidic solution.
Ga, In and TI have lesser tendency to lose electrons #and are thus electropositive%, because of the
poor shielding by d*electrons.
The ,/ values show that the stability of >& o"idation state decreases down the group whereas that
of >1 increases down the group.
Ionisation Energ8
The ionisation energies increase as e"pected #first ionisation energy @ second ionisation energy
@third ionisation energy%. The sum of the first three ionisation energies for each of the elements
is very high. Thus, boron has no tendency to form ions, and always forms covalent bonds. The
other elements normally form covalent compounds e"cept in solution where the high hydration
energy compensates the high ionisation energy.
The ionisation energy values do not decrease smoothly down the group. The decrease from B to
+l is the usual trend on descending a group associated with increased sie. The poor shielding by
d*electrons and the resulting d*bloc! contraction affect the values for the later elements.
1
st
,
nd
9
rd
%um of t2ree
B
+l
Ga
In
TI
1$1
3''
3'.
331
31.
2)2'
1112
1.'.
112$
1.'1
&23.
2'))
2.22
2'$)
21''
211'
31&'
332$
3$12
3)&'
Boron
Page No.-9
Preparation:
"i$ Boron is obtained by the reduction of B
2
O
&
with magnesium or sodium B
2
O
&
is first
prepared by strongly heating 6
&
BO
&
which is obtained by the action of 60l or 6
2
AO
)
on a
concentrated solution of bora":
5a
2
B
)
O
'
> 260l > 36
2
O )6
&
BO
&
> 25a0l
26
&
BO
&
B
2
O
&
> &6
2
O
B
2
O
&
> &7g 2B > &7gO
8ure crystalline boron may be obtained in small 4uantities by the reduction of BBr
&
with
6
2
on a heated metal filament at 12'3*1)'3 B.
"ii$ !odern !et2od
B is obtained these days by the electrolysis of a fused mi"ture containing boric anhydride, 7gO
and
2
7g?
at 11$$/0. The electrolysis is done in a carbon crucible, which acts as anode and ?e
rod is used as cathode. The 7g discharged at cathode reduces
2 &
B O
to B.
2
2 &
27gO 27g O
B O &7g 2B &7gO
+
+ +
B thus obtained is heated electrically in vacuum at 11$$/0, when the impurities are volatilised
off and pure boron is obtained.
"iii$ By thermal decomposition of
&
BI
over red hot tungsten filament #<an +r!el method%
( ) ( )
C
& 2
11'&B
2BI 2B s &I g +
Properties:
P28sial
a% Amall atomic sie
b% Dow electronegativity and hard, absorbs neutron, steel grey in colour. Aome
dissimilarities of boron with other elements of this group are :
i% Boron is a non*metal while all other elements of this group are metals.
ii% Boron forms only covalent compounds, while other elements of this group form
both covalent and ionic compounds.
iii% Boron shows a ma"imum covalency of four, while other elements of this group
show a ma"imum valency of si", absorbs neutron, steel grey in colour. Its density
is 2.&) gmEcc.
C2emial
1. 0rystalline Boron is not active. +morphous Boron reacts.
'$$ 0
2 2 &
)B &O 2B O
+ F
'$$ 0
2
2B 5 2B5
+
2. These above reaction accompanies red flame.
2 & & &
B5 &6 O 6 BO 56 + +
&. +ction in al!alis and acids
Page No.-0
2 2 2
2B 25aO6 26 O 25aBO &6 + + +
2 2 & 2
2B &6 O B O &6 + +
o"idation
2 ) & & 2
2B &6 AO 26 BO &AO + +
o"idation
& & & 2
2B 265O 6 BO 25O + +
). Boron reacts with 7g and conse4uent hydrolysis gives diborane.
& 2
&7g 2B 7g B +
& 2
&0a 2B 0a B +
& 2 2 2 2
7g B 260l &7g0l B 6 + +
2 2 2 & & 2
B 6 26 O 26 BO 26 + +
3. Boron reduces silica and 0O
2
2 2 &
&AiO )B 2B O &Ai + +
2 2 &
&0O )B 2B O &0 + +
Illustration - 1
Chich of the statement is true for the above se4uence of reactions G
#a% H is hydrogen #b% I is B
2
6
2
#c% H and J are ?
2
and B
2
6
2
respectively #d% H is potassium hydro"ide
Ans. "$
Note :
+
2 3
(Z) ( X)
B F BF ;
3 2 6 4
(Y)
8BF 6LiH B H 6 LiBF + +
COMPOUNDS OF BORAN
Diborane (B
2
H
6
)
Preparation: Kiborane can be prepared in almost 4uantitative yields by the reduction of boron
trifluoride etherate #B?
&
.O,t
2
% with lithium aluminium hydride #Di+l6
)
% or
sodium borohydride #5aB6
)
%.
2
,t O
& 2 ) 2 2 ) 2
)B? .O,t &Di+l6 2B 6 &Di+l? ),t O + + +
diglyme
& 2 ) 2 2 ) 2
)B? .O,t &5aB6 2B 6 &5aB? ),t O + + +
Page No.-4
where, diglyme is diethyleneglycol dimethyl ether, #7eO06
2
06
2
%
2
O.
Kiborane can also be prepared by treating 5aB6
)
with conc. 6
2
AO
)
or 6
&
8O
)
:
) 2 ) 2 2 2 2 )
25aB6 6 AO B 6 26 5a AO + + +
) & ) 2 2 2 2 )
25aB6 26 8O B 6 26 25a6 8O + + +
Properties: 1. Kiborane is a colourless gas #b.p., 11&B%. It is rapidly decomposed by water
with the formation of 6
&
BO
&
and 6
2
:
2 2 2 & & 2
B 6 26 O 26 BO 26 + +
2. 7i"tures of diborane with air or o"ygen inflame spontaneously produce large
amount of heat. Kiborane has a higher heat of combustion per unit weight of
fuel than most other fuels. Therefore, it is used as a roc!et fuel.
91
2 2 2 2 & 2
B 6 &O B O &6 O, 6 92123 !L mol + + =
&. 8yrolysis of B
2
6
2
in sealed vessels at temperatures above &'3 B is an
e"ceedingly comple" process producing a mi"ture of various boranes, e.g.,
B
)
6
1$
, B
3
6
.
, B
3
6
11
, B
2
6
1$
, B
2
6
12
and B
1$
6
1)
. By careful control of
temperature, pressure and reaction time, the yield of various intermediate
boranes can be optimised. ?or e"ample, by storing B
2
6
2
under pressure for 1$
days, B
)
6
1$
is produced in 13( yield according to the following e4uation:
2 2 ) 1$ 2
2B 6 B 6 6 +
). Kiborane reacts with ammonia gives inorganic benene
2 2 & & & 2 2
& 2 2 12
# %
+ + B H NH B N H H
inorganicbenzene
Illustration - ,
Chen an inorganic compound #I% having &0 9 2e as well as 2e 9 2e bonds reacts with ammonia
gas at a certain temperature, gives a compound #J%, isostructural with benene. 0ompound #I%
with ammonia at a high temperature produces a substance #H%.
#a% #I% is B
2
6
2
#b% #H% is !nown as inorganic graphite
#c% #J% is B
&
5
&
6
2
#d% #H% is soft li!e graphite
+ns. #a, b, c%
Note: Kiborane, B
2
6
2
, is a compound consisting &092e and 2e 9 2e bonds. B
2
6
2
> 256
&

Low temp.
B
2
6
2

200C
3 3 4
(Y)
B N H
M 256
&
. #J% has structure similar to benene. It is called inorganic
benene.
+
High temp.
2 6 3 X
(Z)
B H NH (BN)
. #H% is a hard substanceN.
3. Kiborane undergoes a facile addition reaction with al!enes and al!ynes in
ether solvents at room temperature to form organoboranes:
2O06 P 06
2
> B
2
6
2
2B#06
2
06
2
O%
&
#6ydroboration Oeaction%
Page No.-5
Illustration - 9
Chich one of the following compounds does not e"ists G
#a% B
2
6
)
#06
&
%
2
#b% B
2
6
&
#06
&
%
&
#c% B
2
6
2
#06
&
%
)
#d% B
2
6#06
&
%
3

+ns. #d%
Note 5ot more than four hydrogen atoms can be substituted by methyl groups in the molecule of B
2
6
2
.
The bridge hydrogen atoms are not to be substituted.
Boric Acid: Orthoboric acid 6
&
BO
&
commonly !nown as boric acid and metaboric acid 6BO
2
,
are two well*!nown and important o"oacids of boron.
Preparation: On a large scale, 6
&
BO
&
is prepared by the action of 60l or 6
2
AO
)
on a
concentrated solution of bora":
2 ) ' 2 & &
5a B O 260l 36 O )6 BO 25a0l + + +
Properties: 1. Boric acid is a fla!y, white crystalline solid.
2. It is moderately soluble in water.
&. Boric acid is a very wea! monobasic acid #pB P ..23%, because it acts as an
electron pair acceptor #Dewis acid% from
9
O6 rather than as a proton donor
#+rrhenius acid%.
9
& & 2 ) &
6 BO 26 O QB#O6% N 6 O
+
+ +

). On heating boric acid at &'3 B, metaboric acid, 6BO
2
is formed. On further
heating above 3$$ B, B
2
O
&
is formed:
&'3 B
& & 2 2
6 BO 6BO 6 O + F
3$$ B
2 2 & 2
26BO B O 6 O +
In solution metaboric acid changes into orthoboric acid.
Borax(Sodium tetraborate decahydrate, Na
2
B
4
O
7
. 10H
2
O)
Preparation: It is obtained by e"tracting impure bora" with water and then concentrating the
solution until crystals of bora" separate out.
Bora" can also be prepared from the mineral colemanite by boiling it with 5a
2
0O
&
solution::
2 2 11 2 & 2 ) ' 2 &
0a B O 25a 0O 5a B O 25aBO 20a0O + + +
Properties: 1. Bora" is a white crystalline solid. It is hydrolysed by water to give an al!aline
solution:
2 ) ' 2 & &
5a B O '6 O )6 BO 25aO6 + +

2. On heating, bora" loses water to become anhydrous. +nhydrous bora" on
strong heating with 56
)
0l gives boron nitride and boron trio"ide:
2 ) ' ) 2 & 2
5a B O 256 0l 2B5 B O 25a0l )6 O + + + +
&. On heating alone, it decomposes to form 5aBO
2
and B
2
O
&
2 ) ' 2 2 &
5a B O 25aBO B O +
Page No.-3
Illustration -0
5a
2
B
)
O
'
M 1$6
2
O is correctly represented as
#a% 25aBO
2
M 5a
2
B
2
O
&
M 1$6
2
O #b% 5a
2
QB
)
O
3
#O6%
)
N M 16
2
O
#c% 5a
2
QB
)
O
3
#O6%
)
N M 1 6
2
O #d% 5a
2
QB
)
#6
2
O%
)
O
'
N M 26
2
O
+ns. #b%
Note Bora" molecule is actually made of two tetrahedra and two triangular units Roined as shown
below :
N a
2
H O ! B
O ! B

! O
O ! B

O
! O
B ! O H
O H
O H
Illustration - 4
+morphous boron is e"tracted from bora" by following steps :
Bora"
(") Heat (B)
3 3 2 3
H BO B O Bo#o$
#a% 6
2
AO
)
, +l #b% 60l, carbon #c% 6
2
AO
)
, 7g #d% 60l, ?e
+ns. #c%
Note 5a
2
B
)
O
'
> 6
2
AO
)
> 36
2
O 5a
2
AO
)
> )6
2
BO
&
F +
2 3 2 3 2
2H BO B O 3H O;
+ +
2 3
B O 3%g 2B 3%gO&
). Bora: ;ead Test: The formation of coloured metaborates by transition metal
salts is used in bora" bead test in 4ualitative analysis. The colour depends on
the o"idising or reducing flame of the bunsen burner.
+ cupric salt forms blue cupric metaborate in the o"idising flame:
5a
2
B
)
O
'
> 0uO 0u#BO
2
%
2
> 25aBO
2

In the reducing flame , #ie. in presence of carbon % the coloured salt is reduced
to colourless cuprous metaborate:
20u#BO
2
%
2
> 25aBO
2
> 0 20uBO
2
> 5a
2
B
)
O
'
> 0O. and to metallic
copper and hence bead becomes dull red and opa4ue.
20u#BO
2
% > )5aBO
2
> 20 20u > 25a
2
B
)
O
'
> 20O
Compounds of
Colour of ;ora: ;ead
<:idising flame 'eduing flame
0hromium Green Green
7anganese +methyst 0olourless
Iron Jellow#cold% Bottle green
0obalt Keep blue Keep blue
5ic!el Brownish#cold% Grey
0opper Green#hot%,blue#cold% 0olourless or red
Page No.-=
Aluminium
Aluminium oxide - Al
2
O
3
(Alumina)
Preparation: In the lab, it is prepared by igniting aluminium hydro"ide, aluminium sulphate or
ammonium alum.
2+l#O6%
&
+l
2
O
&
> &6
2
O
+l
2
#AO
)
%
&
+l
2
O
&
> &AO
&
#56
)
%
2
AO
)
.+l
2
#AO
)
%
&
.2)6
2
O 256
&
> +l
2
O
&
> )AO
&
> 236
2
O
Properties: Chite crystalline powder and it is an amphoteric o"ide.
+l
2
O
&
> 260l 2+l0l
&
> &6
2
O
+l
2
O
&
> 25aO6 25a+lO
2
> 6
2
O
Aluminium Chloride: AlCl
3
.6H
2
O
Preparation: It is prepared by the action of dil or conc. hydrochloric acid on aluminium
2+l > 260l 2+l0l
&
> &6
2
i% +luminium chloride e"ists as dimer #+l
2
0l
2
% in inert solvent as well as in
vapour state.
ii% It is a white crystalline, hygroscopic solid and it fumes in moist air due to
hydrolysis.
+l0l
&
> &6
2
O +l #O6%
&
> &60l
Alums: +lums are the double sulphates having general formula: I
2
AO
)
.7
2
#AO
)
%
&
.2)6
2
O
I P monovalent cation such as 5a
>
, B
>
, 56
)
>
etc.
7 P trivalent cation such as +l
&>
, 0r
&>
, ?e
&>
etc.
when alum contains aluminium as trivalent cation then it is named after monovalent cation.
e.g. B
2
AO
)
.+l
2
#AO
)
%
&
.2)6
2
O potash alum
5a
2
AO
)
.+l
2
#AO
)
%
&
.2)6
2
O * Aoda alum.
Chen trivalent cation is not aluminium then alum is named after both, monovalent as well as
trivalent cation.
#56
)
%
2
AO
)
.?e
2
#AO
)
%
&
.2)6
2
O * ferric ammonium alum.
Illustration - 5
Chich of the following minerals does not contain aluminium G
#a% 0ryolite #b% 7ica #c% ?eldspar #d% ?luorspar
+ns. #d%
Note : 0ryolite 9 5a
&
+l?
2
F ?eldspar 9 B+lAi
&
O
1
S
Q7ica 9 B
2
O M &+l
2
O
&
M2AiO
2
M 26
2
OF ?luorspar 9 0a?
2
N
Page No.->
Illustration - 3
The function of luorspar in the electrolytic reduction of alumina dissolved in fused cryolite
#5a
&
+l?
2
% is
#a% as a catalyst
#b% to lower the temperature of melt and to ma!e the fused mi"ture very conducting
#c% to decrease the rate of o"idation of carbon anode
#d% none of these
Ans. ";$
Illustration - =
+l
2
O
&
can be converted to anhydrous +l0l
&
by heating
#a% a mi"ture of +l
2
O
&
and carbon in dry 0l
2
gas
#b% +l
2
O
&
with 0l
2
gas
#c% +l
2
O
&
with 60l gas
#d% +l
2
O
&
with 5a0l in solid state
Ans. "a$
?int:+l
2
O
&
> &0 > &0l
2
2+l0l
&
> &0ON
Illustration - >
6ydrated +l0l
&
is used as
#a% catalyst in crac!ing of petroleum #b% catalyst in ?riedel*0raftSs reaction
#c% mordant #d% all of these
Ans "$
Illustration - 1-
+l0l
&
on hydrolysis gives
#a% +l
2
O
&
M 6
2
O #b% +l#O6%
&
#c% +l
2
O
&
#d% +l0l
&
M 26
2
O
Ans ";$
Page No.-1-
CA'B<N / @A!IA(
Elements : C, %i, Ge, %n, P;
General eletroni onfiguration :
2 2
ns , np
1. Co7alent radii
The covalent radii increase down the group. The difference in sie between Ai and Ge is less than
might be otherwise e"pected because Ge has a full &d*shell, which shields the nuclear charge
rather ineffectively. In a similar way the small difference in sie between An and 8b is because of
the filling of the )f shell.
0ovalent Oadius
#-%
Ionisation ,nergy #!Lmol
91
%
7elting point
#/0%
Boiling 8oint
#/0%
1
st
2
nd
&
rd
)
th

C
%i
Ge
%n
P;
$.''
1.1'
1.22
1.)
1.)2
1$12
'12
'2$
'$'
'13
2&3)
13'&
13&)
1)$.
1))'
)222
&2&2
&&$$
2.)&
&$1'
222&
)&31
))$.
&121
)$11
)1$$
1)2$
.)3
2&2
&2'
99
&21$
213$
222&
1'31
,. Ionisation energ8
The ioniation energy decrease from 0 to Ai, but then change in an irregular way because of the
effects of filling of the d and f*shells. The amount of energy re4uired to form
)
7
+
ions is
e"tremely large and hence simple ionic compounds are rare.
9. !elting points
7elting involves brea!ing the strong covalent bonds in the lattice of 0 and thus has e"tremely
high melting point. The melting points decrease on descending the group because the 7*7 bonds
become wea!er as the atoms increase in sie. An and 8b are metallic and have much lower
melting points. They do not use all four outer electrons for metallic bonding.
0. !etalli and non-metalli 2arater
The change from non*metal to metal with increasing atomic number is well illustrated in group
I<, where 0 and Ai are non*metals, Ge has some metallic properties, An and 8b are metals. The
increase in metallic character shows itself in the structures and appearance of the elements, in
physical properties such as malleability and electrical conductivity, and in chemical properties
such as the increased tendency to form
2
7
+
ions and the acidic or basic properties of the o"ides
and hydro"ides.
Carbon
Allotropes of carbon: The phenomenon of the e"istence of an element in different forms, which
have different physical properties but similar chemical properties, is !nown as allotropy. such different
forms of an element are called its allotropes or allotropic forms.
The various allotropic forms of carbon can be broadly classified into two classes.
a% Crystalline form: Kiamond and graphite are the two crystalline forms of carbon. Graphite is
thermodynamically more stable than diamond, thermodynamically, diamonds should get transformed
into graphite on their own. But it does not happen at least on our life time scale. This is because, this
conversion is not favoured by !inetic factors, i.e., the activation energy for this reaction is very high.
Page No.-11
;$ Amorphous form:0oal, 0o!e, 0harcoal #or wood charcoal%, animal charcoal #or bone blac!%,
Damp blac!, 0arbon blac!, Gas carbon and 8etroleum co!e are the amorphous form of carbon.
Structure of Diamond: In diamond, the carbon atoms are arranged tetrahedrally
#sp
&
hybridisation of 0%: ,ach 0 atom is lin!ed to its neighbours by four single covalent bonds. This
leads to a three*dimensional networ! of covalent bonds. It is because of this, that diamond is very hard
and has high melting and boiling points. Aince, all the valence electrons of carbon are used up in forming
the covalent bonds, hence diamond does not conduct electricity.
Structure of Graphite: In graphite, the carbon atoms are arranged in regular he"agons in flat
parallel layers. ,ach carbon in these layers is bonded to three other by sp
2
covalent bonds. This gives
some double bond character to graphite. ,ach layer is bonded to the adRacent layers by wea! vander
CaalSs forces. +s a result, each layer can slide over the other easily. It is because of this structure that
graphite is soft and slippery and can act as a lubricant. The presence of double bond character #the
presence of delocalised T*electrons% ma!es graphite a good conductor of electricity.
Oxides: 0arbon burnt in air forms two o"ides, carbon mono"ide, 0O and 0arbon dio"ide 0O
2
.
a)Carbon Monoxide (CO)
Preparation: i% By heating carbon in limited supply of o"ygen.
0 >
2
'
O
2
0O.
ii% By heating o"ides of heavy metals e.g. iron, inc etc with carbon.
?e
2
O
&
> &0 2?e > &0O
HnO > 0 Hn > 0O
Two important industrial fuels water gas and producer gas contain carbon
along with hydrogen and nitrogen, Cater gas is obtained by passing steam
over hot co!e
0 > 6
2
O
2
#water gas%
0O 6 +

Chen air is passed over hot co!e, producer gas is obtained.
20 > O
2
> )5
2

2
#producer gas%
20O )5 +
Properties: i% It is powerful reducing agent and reduces many metal o"ides to the
corresponding metals e.g.
?e
2
O
&
> &0O 2?e > &0O
2
0uO > 0O 0u > 0O
2
ii% It burns in air to give heat and carbon dio"ide
0O >
1
2
O
2
0O
2
> heat.
Tests: a% Burns with blue flame
b% + filter paper soa!ed in platinum or palladium chloride is turned pin!,
green or blac! due to reduction of the chloride by carbon mono"ide.
b)Carbon di-oxide (CO
2
):
Preparation: i% In the lab., it is prepared by the action of acids on carbonates.
Page No.-1,
0a0O
&
> 260l 0a0l
2
> 6
2
O > 0O
2
ii% By combustion of carbon
0 > O
2
0O
2
Properties: i% It turns lime water mil!y and mil!iness disappears when 0O
2
is passed in
e"cess
0a#O6%
2
> 0O
2
0a0O
&
> 6
2
O
0a0O
&
> 6
2
O > 0O
2
0a#60O
&
%
2
ii% Aolid carbon dio"ide or dry ice is obtained by cooling 0O
2
under pressure.
It passes to the solid state straight from gaseous state without li4uefying
#hence dry ice%.
iii% + burning candle is put out but burning magnesium continues burning in
the gas Rar.
Carbides: 0arbon combines with more electropositive elements than itself when heated to high
temperature to form carbides. 0arbides are of mainly three types.
i% Salt like Carbides: These are the ionic salts containing either 0
2
2*
#acetylide ion% or 0
)*
#methanide ion%e.g. 0a0
2
, +l
)
0
&
, Be
2
0.
ii% Covalent Carbides:These are the carbides of non*metals such as silicon and boron. In
such carbides, the atoms of two elements are bonded to each other through covalent bonds.
Ai0 is also !nown as 0arborundum.
iii% Interstitial Carbides: They are formed by transition elements and consist of metallic
lattices with carbon atoms in the interstices. e.g. tungsten carbide C0, vanadium carbide
<0.
Illustration - 11
Graphite is not
#a% a good conductor of heat #b% an amorphous allotrope of carbon
#c% softer than diamond #d% used for ma!ing lubricants
Ans ";$
?int : Graphite is crystalline allotrope of carbonN
Illustration - 1,
Chen heated with concentrated 6
2
AO
)
, B
)
?e#05%
2
gives
#a% 0O #b% 0O
2
#c% #05%
2
and 0O #d% #05%
2
and 0O
2
Ans "a$
?int : B
)
?e#05%
2
> 26
2
AO
)
> 26
2
O 2B
2
AO
)
> ?eAO
)
> &#56
)
%
2
AO
)
> 20ON
Page No.-19
Illustration - 19
The number and type of bonds between two carbon atoms in 0a0
2
are
#a% one sigma and one pi bond
#b% one sigma and two pi bonds
#c% one sigma and one and a half pi bonds
#d% one sigma bond
Ans ";$
?int :
Illustration - 10
C a C O ( ( )
3
H e a t
( " ) ( ( ) ) ( B ) ( g )
) C a # * o $
h e a t
( C ) ( ( ) ) ( + ) ( g )
( C ) ( ( ) ) H O ( , ) ( g )
2

The 0ompound #,% #g% is
#a% 0O #b% 0O
2
#c% 06
)
#d% 0
2
6
2
Ans. "d$
?int :
+
Heat
3
(") (B)
CaCO CaO CO
+ +
Heat
2
(+)
(C)
CaO C CaC CO
+ +
2 2 2 2 2
(,)
CaC 2H O Ca(OH) C H &
Silicon
E:tration: 0ommercial form of silicon is obtained by reduction of AiO
2
with 0 or 0a0
2
in an electric
furnace. 6igh purity silicon is obtained either from Ai0l
)
or from Ai60l
&
. These volatile
compounds are purified by e"haustive fractional distillation and then reduced with very
pure Hn or 7g. The resulting spongy Ai is melted, grown into cylindrical single crystal
and then purified by one refining.
Properties: Ailicon is obtained by the reduction of silica. It e"ists in two allotropic forms: #a%
amorphous and #b% crystalline. The amorphous variety is obtained by heating dry
powdered silica with magnesium.
Page No.-10
2
AiO 27g Ai 27gO + +
1. The crystalline variety is obtained by heating a finely powdered sand or 4uart with
carbon and in electric furnace a small amount of iron is added to prevent the
formation of carborundum #Ai0%.
2
AiO 20 Ai 20O + +
2. +morphous silicon is chemically more reactive than crystalline silicon. +morphous
silicon is brownish powder. It burns brilliantly in o"ygen and ignites spontaneously in
fluorine.
2 2
Ai O AiO +
2 )
Ai 2? Ai? +
&. It decomposes steam at red heat. It dissolves in the mi"ture of 65O
&
and 60l.
6owever, it dissolves readily in al!aline medium.
2 2
Ai 26 O AiO + >26
2
2 )
Ai 2? Ai? +
). It combines with certain metals forming silicides
2
27g Ai 7g Ai +
3. Chen amorphous silicon is strongly heated, it fuses and on cooling solidifies to the
crystalline form. It is very hard crystalline silicon, does not burn in o"ygen but it
readily combines with fluorine. It dissolves in mi"ture of 65O
&
and 6?. Chen fused
with al!ali, it gives a silicate.
2 & 2 &
5a 0O Ai 5a AiO 0 + +
Silicones: Ailicones are a group of organo silicon polymers. Unli!e Ai0l
)
which on complete
hydrolysis gives AiO
2
, al!yl substituted chlorosilanes on hydrolysis do not give the e"pected
silicon compound analogous to !etone but get hydrolysed to long chain polymers or silicones.
Chile the hydrolysis of trial!ylmonochlorosilane yields he"al!yldisilo"ane, the
al!yldichlorosilane gives straight chain polymers with active hydro"yl groups at each end of the
chain and trichlorosilane gives comple" cross*lin!ed polymers. The chain sie is limited by the
sie of al!yl group and the amount of cross*lin!ing is regulated by the relative amounts of di*
and tri*methylchlorosilanes
Ai
O
O
Ai
Ai
O
O O
O
O
O
O
0yclic silicone
Ai
O
O
O
O
Ai
O
O O
0 6
&
0 6
&
O
O
O
O
O
O
06
&
O
06
&
O
0ross lin!ed silicone polymer
Ai
O
O
O Ai
O
O
O Ai
O
O
O
Dinear silicone polymer
Silicates: Ailicates are regarded as the salts of silicic acid, 6
)
AiO
)
. +ll the silicates are
comprised of AiO
)
units. These units have a tetrahedral structure formed as a result of sp
&
hybridistion.
Page No.-14
Ailicon atom has its complete octet but each o"ygen atom is still short of
one electron to complete its octet. They can complete their octet by ta!ing
up ) electrons from a metal, getting converted to an anion QAiO
)
N
)9
.
O Ai
O
O
O
The QAiO
)
N
)9
tetrahedral can be represented in three ways
Ai
O O
O
O
O O
O
O
O
O
'epresentations of
)9
)
AiO tetra2edra
In some silicates, the o"ygen atoms of AiO
)
units tend to complete their octet by sharing
electrons with other silicon atoms, the o"ygen atoms, thus, form bridges of the type AiVOVAi to
other silicon atoms. The number of such bridges can vary from one to four. This leads to the
formation of comple" silicates. +ny o"ygen which fails to pic! up electrons from the other
silicon atom is not able to complete its octet. The resulting silicate chains are, therefore,
negatively charged anions. The metal cations generally present in silicate minerals are Di
>
, 5a
>
,
B
>
, 0a
2>
, +l
&>
, etc. Kepending upon the way these AiO
)
units are lin!ed, silicates of different
structure and comple"ity are obtained. Aome representative types are:
#a% pyrosillicate #b% cyclic silicate #c% chain silicate
#d% sheet silicate
Silicon Carbide or (Carborundum)
Preparation: Ai0 is made commercially by reducing silicon with carbon in an electric
resistance furnace.
AiO
2
> &0 Ai0 > 20O
Properties: It is e"tremely hard and is very difficultly fusible #does not decompose below
22$$
o
0%
Page No.-15
It resists most chemical reagents but is o"idised by fused 5aO6 in contact with
air.
Ai0 > )5aO6 > 2O
2
5a
2
0O
&
> 5a
2
AiO
&
> 26
2
O
In Ai0, carbon and silicon atoms are alternate and are each surrounded
tetrahedrally. It is widely used as an abrasive for grinding, cutting and polishing.
Illustration - 14
Chich of the following is correct G
#a% Ailicones are organosilico polymers containing Ai V O V Ai lin!age
#b% O
&
Ai0l on hydrolysis gives O
&
Ai V O V AiO
&
#c% Both of these
#d% Both #b% and #c%
Ans. "$
Illustration - 15
In silicon dio"ide
#a% each silicon atom is surrounded by four o"ygen atoms and each o"ygen atom is bonded to two
silicon atoms
#b% each silicon atom is surrounded by two o"ygen atoms and each o"ygen atom is bonded to two
silicon atoms
#c% silicon atom is bonded to two o"ygen atoms
#d% there are double bonds between silicon and o"ygen atoms
Ans. "a$
?int : Q ,ach silicon atom is surrounded tetrahedrally by four o"ygen atoms
- -
- -
- -
O O
!O!.i !O !.i ! O !&
O O
- -
Illustration - 13
The compound #0% is
#a% AiO
2
#b% Ai #c% Ai0 #d% 5a
2
AiO
&
Ans. "d$
Page No.-13
?int: Q
+
2 3
Na CO Heat
4 2 4 2 2 3
Heat
(") (C)
.iC/ H O .i(OH) .iO Na .iO &
Illustration - 1=
Chen a mi"ture of air and steam is passed over red hot co!e, the outgoing gas contains
#a% producer gas #b% water gas
#c% coal gas #d% mi"ture of #a% and #b%
+ns. #d%
?int:
+ + + +
2 2 2
0# o123e# ga( .team 4ate# ga(
Co5e ai# CO N ; Co5e H O CO H &
<:ides and C2lorides of Tin
%tannous <:ide "%n<$
( )
2
2
Atan nous
chloride
An0l 25aO6 An O6 25a0l + +
2
6eat in0O +tmosphere
2 2
An#O6% AnO 6 O +
2
6eat inatmof 0O
2 2 & 2
An0l 5a 0O AnO 0O 25a0l + + +
Atan nous
chloride
Properties
#i% It is a grey or blac! power. It is insoluble in water.
#ii% It is brns in air with incandescence forming stannic o"ide,
2
AnO
.
2 2
2AnO O 2AnO +
#iii% It is an amphoteric o"ide. It dissolves both in acids and al!alies.
2 2
Atan nous
chloride
AnO 260l An0l 6 O + +
2 2 2
sodium stannite
AnO 25aO6 5a AnO 6 O

+ +
Atannites are !nown only in a4ueous solutions. Atannites absorb o"ygen from air and are
o"idied to stannates which are stable in nature.
2 2 2 2 &
25a AnO O 25a AnO
Sodium stannate
+

%TANNIC <BI)E ( )
2
AnO
It is found in nature as 0assiterite or tin stone.
Preparation
2 2
An O AnO
+
& 2 & 2 2
An )65O 6 AnO )5O 6 O + + +
2 & 2 2
6 AnO AnO 6 O
Metastannic acid
+
Page No.-1=
Properties
It is a white powder, insoluble in water. It is somewhat unreactive. 6owaver, it dissolves in
concentrated
2 )
6 AO
forming stannic sulphate.
2 2 ) ) 2 2
AnO 26 AO An#AO % 26 O + +
Chen the solution is diluted, stannic o"ide is reprecipitated.
( )
) 2 2 2 )
2
An AO 26 O AnO 26 AO + +
It readily dissolves in al!alies forming stagnates.
2 2 & 2
AnO 2BO6 B AnO 6 O + +
%tannous 2loride " ( )
2
An0l
Preparation
#i% 6ydrated stannous chloride
2 2
An0l .26 O
is prepared by dissolving tin in hot concentrated
hydrochloric acid and subRecting the solution to crystalliation.
2 2
An 260l An0l 6
+ +
6ydrated stannous chloride consists of two molecules of water as water of crystalliation
2 2
#An0l .26 O%.
+nhydrous salt cannot be obtained by heating the hydrated salt as it undergoes hydrolysis
and a white solid of tin hydro"yl chloride is formed.
2 2 2
An0l .26 O An#O6%0l 60l 6 O + +
It can also be obtained when a mi"ture of An and calculated 4uantity of mercuric chloride
is heated.
2 2
An 6g0l An0l 6g + +
Properties
#i% It is a white crystalline solid. It is soluble in water, alcohol and ether.
#ii% In water, it is soon hydrolysed. 6owever in presence of 60l #acid%, hydrolysis is revered.
#iii% It forms a white precipitate with al!alies. The precipitate of stannous hydro"ide, however,
dissolves in e"cess of al!ali.
2 2
An0l 25aO6 An#O6% 25a0l + +
2 2 2 2
An#O6% 25aO6 5a AnO 26 O + +
#iv% It forms a dar! brown precipitate of stannous sulphide on passing
2
6 A
through its
solution. The precipitate dissolves in yellow ammonium sulphide.
2 2
An0l 6 A AnA 260l + +
) 2 2 ) 2 &
Jellowammonium +mmoniumthios tannate
Aulphide
AnA #56 % A #56 % AnA +
#v% It is a strong reducing agent. ?ew e"amples are given below:
#a% It reduces mercuric chloride to mercurous chloride #white ppt% and finally to metallic
mercury #dar! grey or blac!%
2 2 2 2 )
7ercurouschloride
26g0l An0l 6g 0l An0l + +
2 2 2 )
6g 0l An0l 26g An0l + +
#b% It reduces ferric salts to ferrous salts and cupric salts into cuprous salts.
& 2 2 )
2?e0l An0l 2?e0l An0l + +
2 2 )
20u0l An0l 20u0l An0l + +
#c% It decolourises iodine and thus can be titrated with it.
Page No.-1>
2 2 )
An0l 260l I An0l 26I + + +
#d% Organic nitro compounds are reduced to amino compounds.
2 3 2 2 2 3 2 ) 2
5itrobenene +niline
0 6 5O 260l &An0l 0 6 56 &An0l 26 O + + + +
#e% Its reduces gold chloride to metallic gold.
& 2 )
0olloidalgold
2+u0l &An0l 2+u &An0l + +
An0l
)
undergoes hydrolysis forming stannic acid which absorbs colloidal particle of gold
and thus forms purple of cassius.
%tanni 2loride
)
#An0l %
Preparation
2 )
An 20l An0l +
Properties
#i% It is a colourless fuming li4uid having disagreeable smell.
#ii% It is hygroscopic and forms crystalline hydrates containing &, 3, 2 and 1 molecules
of water as water of crystalllisation. The pentahydrate
) 2
An0l .36 O,
is !nown as
Wbutter of tinX or Wo"ymuriate of tinX.
#iii% It is soluble in water in which it undergoes hydrolysis.
An0l
)
)6
2
O
An #O6%
)
> )60l
It is also soluble in organic solvents showing that it is a covalent compound.
#iv% It dissolves in concentrated 60l forming chlorostannic acid. In presence of
ammonium chloride, it forms ammonium salt of this acid.
An0l
)
> 260l 6
2
An0l
2
0hlorostannic acid
An0l
)
> 256
)
0l #56
)
%
2
An0l
2
+mmounium chlorostannate
<:ides and C2lorides of Aead
Aead !ono:ide "P;<$
It is !nown in two forms:
#i% a yellow powder commonly !nown as massicot and
#ii% a buff coloured crystalline form !nown as litharge.
Preparation
It is obtained by heating lead or lead sulphide in air at &$$/0 #massicot form%. Chen the
temperature of o"idation is !ept at .$$/0, litharge is formed.

2
28b O 28bO +
2 2
28bA &O 28bO 2AO + +
It is also formed by heating lead nitrate or lead carbonate.
( )
& 2 2
2
28b 5O 28bO )5O O + +

& 2
8b0O 8bO 0O +
Properties
It is insoluble in water. It is an amphoteric o"ide. It dissolves both in acids and al!alies.
( )
& & 2
2
8bO 265O 8b 5O 6 O + +
2 2 2
8bO 25aO6 5a 8bO 6 O + +
Page No.-,-
On heating in air at )'$/0, it forms red lead.
2 & )
28bO O 28b O + #red lead%
'E) AEA) ( )
& )
8b O
Preparation
It is obtained by heating litharge at )'$/0 in air.
o
)'$ 0
2 & )
28bO O 28b O +
8roperties
It is a red powder, insoluble in water. Chen heated, it becomes almost blac!, but it again
becomes red on cooling. On heating above )'$/0, it decomposes into 8bO and
2
O
.
& ) 2
28b O 28bO O +
Chen treated with concentrated
&
65O
, lead nitrate and brownish blac! insoluble o"ide,
2
8bO
,
are formed. This indicates that
& )
8b O
is a compound o"ide containing both
2
8bO
and 8bO in
the ratio of 1 : 2
( )
& ) & & 2 2
2
8b O )65O 28b 5O 8bO 26 O + + +
Cith
2 )
6 AO
, it evolves o"ygen,
& ) 2 ) ) 2 2
28b O 26 AO 28bAO 26 O O + + +
It acts as an o"idising agent.
& ) 2 2 2
& )
& ) 2
8b O 160l &8b0l )6 O 0l
8b O )0 &8b )0O
8b O )0O &8b )0O
+ + +
+ +
+ +
AEA) C?A<'I)E ( )
2
8b0l
It is made by adding hydrochloric acid to a cold solution of lead salt.
( )
& 2 &
2
8b 5O 260l 8b0l 265O + +
It is only slightly soluble in cold water, but appreciably soluble in hot water. It dissolves in
concentrated 60l forming a comple" ion.
( )
2 2 )
0hloroplumbous acid
8b0l 260l 6 8b0l +

Note
7ost of the plumbic compound are unimportant because they decompose readily on heating and
are hydrolysed to
2
8bO
by even cold water. +n e"ception is tetraethyl lead, ( )
2 3
)
8b 0 6
, a
colourless li4uid which is used as an anti*!noc! agent in petrol.
Page No.-,1
NIT'<GEN @A!IA(
T?E NIT'<GEN @A!IA(
Group 13 includes nitrogen phosphorus, arsenic, antimony and bismuth. +s we go down the group, there
is a shift from non*metallic to metallic through metalloidic character. 5itrogen and phosphorus are non*
metal, arsenic and antimony metalloid and bismuth is a typical metal.
Eletroni Configuration:
The valence shell electronic configuration of these element is ns
2
np
&
the s orbital in these element is
completely filled and p orbitals are half* filled, ma!ing their electronic configuration e"tra stable.
Atomi and Ioni 'adii:
0ovalent and ionic #in a particular state% radii increase in sie down the group. There is a considerable
increase in covalent radius from 5 to 8. 6owever, from +s to Bi only a small increase in covalent radius
is observed. This is due to the presence of completely filled d and E or f orbitals in heavier members.
Ionisation Ent2alp8:
Ionisation enthalpy decreases down the group due to gradual increase in atomic sie. Because of the
e"tra stable half* filled p*orbital electronic configuration and smaller sie, the ionisation enthaply of the
group 13 element is much greater than of group 1) elements in the corresponding periods. The order of
successive ionisation enthalpies, as e"pected is
1 2 &
6 6 6 < <
Eletronegati7it8:
The electronegativity value, in general, decreases down the group with increasing atomic sie. 6owever,
amongst the heavier elements, the difference is not that much pronounced.
P28sial Properties:
+ll the elements of this group are polyatomic. Kinitrogen is a diatomic gas while all others are solids.
7etallic character increases down the group. 5itrogen and phosphours are nonVmetals, arsenic and
antimony metalloids and bismuth is a metal. This is due to decrease in ionisation enthalpy and increase
in atomic sie. The boiling points, in general increase from top to bottom in the group but the melting
point increases upto arsenic and then decreases upto bismuth. ,"cept nitrogen, all the elements show
allotropy.
Element N P As %; Bi
+tomic 5umber ' 13 && 31 1&
+tomic 7ass 1).$1 &$..' ')..2 121.'2 2$1..1
,lectronic
configuration
[ ]
2 &
6e 2s 2p
[ ]
2 &
5e &s &p
[ ]
1$ 2 &
+r &d )s )p
[ ]
1$ 2 &
Br )d 3s 3p
[ ]
1$ 2 &
Ie )d 3s 3p
0ovalent
OadiusEpm
'$ 11$ 12$ 1)$ 13$
Ionic Oadius Epm
& &
a 7 , b 7
+
= =
1'1
a
212
a
222
a
'2
b
1$&
b
Ioniation
enthalpy Y
( )
1
!L mol
I 1)$2 1$12 .)' 1&) '$&

II 2132 1.$& 1'.1 13.3 121$
III )3'' 2.1$ 2'&2 2))& 2)22
,lectronegativity &.$ 2.1 2.$ 1.. 1..
Page No.-,,
C2emial Properties :
O"idation Atates and trends in a chemical reactivity:
The common o"idation states of these elements are 9&, >& and >3. The tendency to e"hibit 9& o"idation
state decreases down the group, bismuth hardly forms any compound in 9& o"idation state. The stability
of >3 o"idation state decreases down the group. The only well characteried Bi#<% compound is
3
Bi?
.
The stability of >3 o"idation state decreases and that of >& state increases #due to inert pair effect% down
the group.
& & & 3 3 3
Bi Ab +s F Bi Ab +s
+ + + + + +
> > < <
5itrogen e"hibits >1, >2, >), >3 o"idation states also when it reacts with o"ygen. 8hosphours also
shows >1 and >) o"idation states in some o"oacids.
In the case of nitrogen, all o"idation states from >1 to >) tend to disproportionate in acid solution.
?or e"ample,
2 & 2
&65O 65O 6 O 25O + +
Aimilarly, in case of phosphorus nearly all intermediate o"idation states disproportionate into >3 and 9&
both in al!ali and acid. 6owever >& o"idation state in case of arsenic, antimony and bismuth become
increasingly stable with respect to disproportionation.
5itrogen is restricted to a ma"imum covalency of ) since only four #one s and three p% orbitals are
available for bonding. The heavier elements have vacant d orbitals in the outermost shell which can be
used for bonding #covalency% and hence, e"pand their covalence as in
2
8?
.
Oeactivity towards hydrogen :
+ll the elements of Group 13 form hydrides of the type
&
,6
where , P 5, 8, +s, Ab or Bi. Aome of the
properties of these hydrides are shown in Table. The hydrides show regular gradation in their properties.
The stability of hydrides decreases from
&
56
to
&
Bi6
which can be observed from their bond
dissociation enthalpy. 0onse4uently, the reducing character of the hydrides increases. +mmonia is only a
mild reducing agent while
&
Bi6
is the strongest reducing agent amongst all the hydrides. Basicity also
creases in the order
& & & & &
56 86 +s6 Ab6 Bi6 > > >
P'<PE'TIE% <@ ?()'I)E% <@ G'<CP 14 EAE!ENT%
8OO8,OTJ
&
56
&
86
&
+s6
&
Ab6
&
Bi6
7elting point E B 1.3.2 1&..3 132.' 113 9
Boiling point E B 2&1.3 113.3 21$.2 23).2 2.$
#,96% Kistance E pm 1$1.' 1)1.. 131.. 1'$.' 9
6,6 angle #/% 1$'.1 .&.2 .1.1 .1.& 9
1
f
6 E !L mol

9 )2.1 1&.) 22.) 1)3.1 2'1

( )
1
diss
6 , 6 E !L mol

&1. &22 2.' 233 9
%trengt2 of o:oaids of group DB elements
?or an o"idation state of >3, the strengths of various acids of group 13 elements follow the order,
& & ) & ) & )
65O 6 8O 6 +sO 6 AbO > > >
?or the o"yacids involving the same element in different o"idation states, the strength of an acid
depends upon the number of unhydrogenated o"ygen atoms attached to the central atom. ?or
Page No.-,9
e"ample, for the o"yacids of the type ( )
n
m
O6 HO
, the acid strength varies directly with the
value of n. Thus, nitric acid ( )
&
65O
is stronger than nitrous acid ( )
2
65O
.
The acids
& 2 & & & )
6 8O , 6 8O and 6 8O
are appro"imately of e4ual strength, because all these
acids contain only one unhydrogenated o"ygen atom each. The order of acid strength is
& 2 & & & )
6 8O 6 8O 6 8O > >
Nitrogen
Preparation: 1.
) 2 2 2
56 5O 5 26 O
+
Aince ammonium nitrite is very unstable, it cannot be !ept as such. 6ence nitrogen is
usually prepared by heating a mi"ture of ammonium chloride and sodium nitrite.
) 2 ) 2
56 0l 5a5O 56 5O 5a0l
+ +
) 2 2 2
56 5O 5 26 O
+
2. By heating ammonium dichromate: +mmonium dichromate on heating decomposes
to give nitrogen gas.
) 2 2 ' 2 2 2 &
#56 % 0r O 5 )6 O 0r O
+ +
& 2 2
256 &0uO 5 #g% &0u &6 O
+ + +
2 2 2 2 2 2
56 0O56 265O 25 0O &6 O + + +
2 2
5a5O 60l 5a0l 65O + +
2 2 2 2 2 2
56 0O56 265O &6 O 0O 25 + + +
@i:ation of atmosp2eri nitrogen in 8anamide fertili&er "T2e 8anamide proess$
5itrogen is also fi"ed as calcium cyanamide on heating it with calcium carbide at 1$$$/0
in an electric furnace.
electric furnace
2 2 2
calciumcarbide calciumcyanamide
0a0 5 0a05 0 + +
The mi"ture of calcium cyanamide and carbon #trade name nitrolim% is an important
fertilier.
0alcium cyanamide may also be used as a source of ammonia. The ammonia so produced
can be converted into useful fertiliers. 0alcium cyanamide is decomposed by water to
give ammonia.
2 2 & &
0a05 &6 O 0a0O 256 + +
& 2 ) ) 2 )
256 6 AO #56 % AO +
& 2 ) ) 2 )
256 6 AO #56 % AO +
2 3 & 2 ) & )
8 O 256 &6 O 2#56 % 8O + +
2 2 2 &
0a0l 156 0a0l .156 +
Page No.-,0
Illustration - 1>
+mmonia will be obtained in
#a% 0a05
2
> 6
2
O #b%

Heat
4 2 4
NH H 0O
#c% Both of these #d% 5one of these
Ans "$
?int: Q + +
2 2 3 3
CaCN 3H O CaCO 2NH ; + +
4 2 4 3 3 2
NH H 0O NH H0O H O&
Illustration - ,-
Chich one of the following compounds on strong heating evolves ammonia gas G
#a% #56
)
%
2
0r
2
O
'
#b% 56
)
5O
&
#c% 56
)
5O
2
#d% #56
)
%
2
AO
)
Ans "d$
?int: Q
4 2 2 6 2 3 3 2
(NH ) C# O N ; NH NO N O;
3 2 2 4 2 4 3
NH NO N ; (NH ) .O NH &
Oxides of Nitrogen
@ormula Name Colour 'emar1s
52O 5itrous o"ides 0olourless Oather unreactive
5O 5itric o"ide 0olourless 7oderately reactive
52O& Kinitrogen trio"ide Kar! blue ,"tensively dissociated as gas
5O2 5itrogen dio"ide Brown 7oderately reactive
52O) Kinitrogen tetro"ide 0olourless
,"tensively dissociated to 5O2 as gas and
partly as li4uid
52O3 Kinitrogen pento"ide 0olourless unstable as gasF ionic solid
5O&, 52O2 5ot well characteried and 4uite unstable
Preparation: 1. 5
2
O is obtained generally by heating 56
)
5O
&
:
) & 2 2
56 5O 5 O 26 O +
5
2
O is also !nown as laughing gas because it induces laughter mi"ed with 5
2
.
It is used as an anesthetic by dentists
2. 5O is best prepared by the reduction of 65O
&
with reducing agents li!e 0u or
by reduction of nitrous acid or nitrites by ?e
2>
of
I
9
ions:
& & 2 2
&0u 165O 20u#5O % 25O )6 O + + +
2 ) 2 )
) 2 ) & 2
25a5O 2?eAO &6 AO
25a6AO ?e #AO % 25O 26 O
+ +
+ + +
2 2 ) ) 2 2
25a5O 25aI )6 AO )5a6AO 25O I 26 O + + + + +
Page No.-,4
5O is formed as an intermediate in the manufacture of nitric acid by o"idation
of 56
&
.
&. 5
2
O
&
is obtained as an intense blue li4uid or a pale blue solid on cooling an
e4uimolar mi"ture of 5O and 5O
2
:
2 2 &
5O 5O 5 O +
On warming, its colour fades due to its dissociation into these two o"ides.
). 5O
2
can be prepared by reduction of conc. 65O
&
with 0u or by heating heavy
metal nitrates:
& & 2 2 2
0u )65O 0u#5O % 25O 26 O + + +
& 2 2 2
28b#5O % 28bO )5O O + +
3. 5
2
O
3
is an anhydride of 65O
&
. It is best prepared by dehydrating 65O
&
with
8
)
O
1$
at low temperatures:
23$ B
& ) 1$ 2 3 &
)65O 8 O 25 O )68O + +
Properties: O"ides of nitrogen are all o"idiing agents. 5
2
O even support the combustion of A
and 8. 5O which is thermally more stable, supports the combustion of 7g and 8
but not of A. Aulphur flame is not hot enough to decompose it 5
2
O and 5O are
neutral, while the other o"ides are acidic.
Di4uid 5
2
O
)
undergoes self*ionisation to form 5O
>
and
9
&
5O ions and therefore,
it has been e"tensively studied as a non*a4ueous solvent. Aolid 5
2
O
3
e"ists in the
ionic form,
9
2 &
5O 5O
+
. In the gaseous form, the discrete 5
2
O
3
molecules have a 5
VOV5 bond angle close to 11$/.
Oxyacids: The most important o"o*acid of nitrogen is nitric acid 65O
&
Preparation: i% In the lab, it is prepared by heating 5a5O
&
or B5O
&
with conc. sulphuric acid
in a glass retort.
5a5O
&
> 6
2
AO
)
5a6AO
)
> 65O
&
ii% It is manufactured by the catalytic o"idation of ammonia and the process is
!nown as Ostwald process
)56
&
> 3O
2

8t Oh E
)5O > 26
2
O
25O > O
2

112$B
25O
2
&5O
2
> 6
2
O 265O
&
> 5O.
Properties: i% In a4ueous solution, nitric acid is a strong acid and dissociates to give
hydronium and nitrate ions.
65O
&
> 6
2
O 6
&
O
>
> 5O
&
*
ii% Ation on metals: 0onc. nitric acid is a strong o"idising agent and attac!s
most metals e"cept noble metals such as gold and platinum. The product of
reduction depend upon the concentration of the acid, temp and the nature of
Page No.-,5
the material undergoing o"idation. Cith dilute nitric acid the principle product
is nitric o"ide 5O and with conc. nitric acid, the principle product is 5#I<%
o"ides
&0u > 165O
&
&0u#5O
&
%
2
> 25O > )6
2
O
#dilute%
0u > )65O
&
0u#5O
&
%
2
> 25O
2
> 26
2
O
Hinc, which is a more powerful reducing agent than copper, reacts with dilute
nitric acid to give ammonium nitrate.
)Hn > 1$65O
&
)Hn#5O
&
%
2
> 56
)
5O
&
> &6
2
O
5itric acid also o"idises non * metals and their compounds. Iodine is o"idied to
iodic acid, carbon to carbon dio"ide, sulphur to 6
2
AO
&
and 6
2
AO
)
and phosphorus
to phosphoric acid. 5itric acid is reduced to nitrogen dio"ide #5O
2
%
I
2
> 1$65O
&
26IO
&
> 1$5O
2
> )6
2
O
0 > )65O
&
0O
2
> 26
2
O > )5O
2
1E1 A
1
> 265O
&
6
2
AO
)
> 25O
2
> 26
2
O
8
)
> 2$65O
&
)6
&
8O
)
> 2$5O
2
> )6
2
O
Illustration - ,1
0opper metal on treatment with dilute 65O
&
produces a gas #I%. #I% when passed through acidic
solution of stannous chloride, a nitrogen containing compound #J% is obtained #J% on reaction with
nitrous acid produces a gas #H%. Gas #H% IA
#a% 5O #B% 5
2
#0% 5O
2
#K% 5
2
O
+ns. #d%
Page No.-,3
?int :
+
2 2
.$C/ 7 HC/ HNO
3 2 2
(X)
(Y) (Z)
8C2 1i/. HNO NO NH OH9 HC/ N O&
Illustration - ,,
5itrogen forms 5
2
but phosphorus is converted into 8
)
from 8
2
. The reason for this is
#a% triple bond is present between phosphorus atoms
#b% p*p bonding is wea!
#c% p*p bonding is strong
#d% multiple bond is formed easily
Ans. ";$
Illustration - ,9
Chen +g5O
&
is heated strongly, the products formed are
#a% 5O and 5O
2
#b% 5O
2
and 5
2
O
#c% 5O
2
and O
2
#d% 5O and O
2
+ns. #c%
Phosphorous
E:tration: It is a very reactive element, so it does not occur free in nature. Kifferent ores are:
8hosphorite : 0a
&
#8O
)
%
2
?luorapatite : &0a
&
#8O
)
%
2
0a?
2
0hlorapatite: &0a
&
#8O
)
%
2
. 0a0l
2
8hosphorous is obtained by heating bone ash or phosphorite roc! 0a
&
#8O
)
%
2
with sand
#AiO
2
% and co!e #c% in an electric furnance at about 1''$ B. The reactions are as the
following:
& ) 2 2 ) 1$ &
20a #8O % 2AiO 8 O 20aAiO + +
) 1$ )
8 O 1$0 8 #v% 1$0O + +
Properties: i% 'eation .it2 o:8gen: Jellow phosphorus readily catches fire in air giving dense
white fumes of phosphorus pentao"ide. Oed phosphorus combines with o"ygen only
on heating. Both of them form either phosphorus trio"ide or phosphorus pentao"ide.
heat
) 2 2 &
red phosphorous phosphorus trio"ide
8 &O 28 O +
heat
) 2 2 3
red phosphorus phosphorus pento"ide
8 3O 28 O +
ii% 'eation .it2 2lorine: 8hosphorus reacts with chlorine gas to form tri and
pentachlorides. Jellow phosphorus reacts violently at room temperature, whereas red
phosphorus reacts on heating only.
Page No.-,=
) 2 &
phosphorus trichloride
8 20l )80l +
) 2 3
phosphorus pentachloride
8 1$0l )80l +
iii% 'eation .it2 al1alies "sodium6potassium 28dro:ide$: Jellow phosphorus
dissolves in caustic soda on boiling under an inert atmosphere liberating phosphine.
boil
2 & 2 2
yellow phosphorus sodiumhypophosphite phosphine
)8 &5aO6 &6 O 86 #g% &5a6 8O + + +
iv% Oeaction with nitric acid
8hosphorus gets o"idied by nitric acid to phosphoric acid.
) & & ) 2 2
phosphoric acid
8 2$65O )6 8O 2$5O )6 O + + +
v% Cith metals
8hosphorus reacts with metals forming phosphides. ?or e"ample
) & 2
magnesiumphosphide
27g 8 27g 8 +
Allotropes: 8hosphorus e"ists in the following five different allotropic forms.
i% Chite #yellow% phosphorus is e"tremely reactive.
ii% Below 1$$/0, its vapor density corresponds to the formula 8
)
. +bove 1'$$/0, it
e"ists as 8
2
.
iii% Kue to is low ignition temperature #Z&$/0%, it undergoes
o"idation in the presence of air which slowly raises its
temperature and after a few moments it catches fire
spontaneously. Kue to this reason, it is stored under water.
8 8
8
8
'ed P2osp2orus: Oed phosphorus is stable allotrope at room temperature. Oed
phosphorus is formed by heating white phosphorus in the absence of air at about 23$/0.
It is not poisonous. It is safe to handle because it does not burn spontaneously at room
temperature.
8 8
8
8
8 8
8
8
%truture of red p2osp2orus
1. Oxides:Two important o"ides of phosphorus are :
1. 8hosphorus trio"ide * 8
)
O
2
, also called phosphorous o"ide or phosphorus #III% o"ide
2. 8hosphorus pento"ide * 8
)
O
1$
, also called as phosphoric o"ide or phosphorus #<% o"ide
Page No.-,>
a)Phosphorous trioxide (P
4
O
6
):
Preparation: 8repared by burning white phosphorus in limited supply of air
8
)
> &O
2
8
)
O
2
Properties: i% On heating in air, it forms phosphorus #<% o"ide
8
)
O
2
> 2O
2
8
)
O
1$
ii% Oeacts with water as follows :
8
)
O
2
> 26
2
O #cold% )6
&
8O
&
8hosphorous acid
8
)
O
2
> 26
2
O #hot% &6
&
8O
)
> 86
&
b)Phosphorous Pentoxide (P
4
O
10
)
Preparation: 8repared by burning white phosphorus in e"cess of air or o"ygen
8
)
> 3O
2
8
)
O
1$
Properties: i% Because of its great affinity for water, it acts as a dehydrating agent.
265O
&
> 8
)
O
1$
25
2
O
3
> )68O
&
26
2
AO
)
> 8
)
O
1$
2AO
&
> )68O
&
ii% Oeacts with water as follows:
8
)
O
1$
> 26
2
O #cold% )68O
&
8
)
O
1$
> 26
2
O #hot% )6
&
8O
)
Structure of P
4
O
6
& P
4
O
10

P
O

P
O

O

P
166 pm
100
127
O
O

O

P
P
O
P
O
O
P
160 pm
102
143 pm
123
O
O
O
O
O
O
O
P
2. Oxoacids of Phosphours: 8hosphorus forms two series of o"oacids, the phosphoric and
the phosphorous acids. The o"idation state of phosphorus is >3 in phosphoric acids whereas it is
>& in phosphorous acids.
Page No.-9-
Oxoacids of phosphorus and their properties
Aid Nature Preparation Anion 'emar1s
& 2
6 8O
or
2
6 8#O6%O

6ypophosphorous
crystalline
white solid
white 8) > al!ali
9
2 2
6 8O
hypophosphite
strongly reducing,
monobasic pB Z 2
& &
6 8O
or
2
68O#O6%

Orthophosphorous
deli4uescent
colourless
solid
8)O2 or 80l& > 62O
9 29
2 & &
6 8O , 68O
phosphite
reducing, but slow,
dibasic
1
pB Z 2
2
pB Z 2
6)82O&
8yrophosphorous
white solid 80l& > 6&8O&
29
2 2 3
6 8 O
pyrophosphite
reducing, dibasic
6)82O2
6ypophosphoric
white solid red 8 > al!ali
)9
2 2
8 O hypophosphate
not reducing or
o"idiing, tetrabasic
1
pB Z 2
6&8O)
Orthophosphoric
white solid 8)O1$ > 62O
9 29
2 ) )
6 8O , 68O ,
&9
)
8O , phosphate
not o"idiing, tribasic
6)82O'
8yrophosphoric
colourless
solid
heat phosphates or
phosphoric acid
)9
2 '
8 O pyrophosphate tetrabasic
1
pB Z 2
68O&
7etaphosphoric
deli4uescent
solid
heat 6&8O) to 2$$ B
+ large number of condensed phosphoric acids or their salts are !nown which have rings or chains of
8O
)
tetrahedrally lin!ed through 8*O*8 lin!ages, e.g., di or pyrophosphoric acid, 6
)
8
2
O
'
and
triphosphoric acid, 6
3
8
&
O
1$
.
O 6 8
O
O 8
O
O6
O6 O6
Triphosphoric acid
O 6 8
O
O 8
O
O
O6 O6
8
O
O6
O6
Kiphosphoric acid
Aodium salt of triphosphoric acid, 5a
3
8
&
O
1$
, forms stable chelate comple"es with al!aline earth metal
cations. It is, therefore, used in water softening. Chat is !nown as metaphosphoric acid and given the
empirical formula 68O
&
is in fact a mi"ture of cyclo*polyphosphoric acids containing V8VOV8VO
V lin!ages. Two important cyclo*polyphosphoric acids are cyclotriphosphoric acid, 6
&
8
&
O
.
and cyclo*
tetraphosphoric acid, 6
)
8
)
O
12
.
Page No.-91
O 6 8
O
O 8
O
O6
O O
8 O 6 O
O
8
O
O6
cyclo*triphosphoric acid 0yclo*tetraphosphoric acid
O
8
8
O
8
O
O 6
O O
O6
O O 6
3. Phosphine, PH
3:
8hosphine, 86
&
, is the most stable hydride of phosphorus. It is intermediate
in thermal stability between ammonia and arsine.
Preparation 1. 6ydrolysis of metal phosphides such as +l8 or 0a
&
8
2
:
& 2 2 & 2
0a 8 26 O 286 &0a#O6% + +
2. 8yrolysis of phosphorous acid at )1$ 9 )13 B:
& & & & )
)6 8O 86 &6 8O +
&. +l!aline hydrolysis of phosphonium iodide:
) & 2
86 I BO6 86 BI 6 O + + +
). +l!aline hydrolysis of white phosphorus #industrial process%:
) 2 & 2 2
8 &BO6 &6 O 86 &B6 8O + + +
8hosphine is a colourless, e"tremely poisonous gas having a faint garlic odour. +s the
896 bond is not polar enough to form 896****8 or 8*6****O bonds, unli!e ammonia,
phosphine is not associated in the li4uid state and is much less soluble in water. In
contrast to the basic nature of solutions of ammonia in water, a4ueous solutions of
phosphine are neutral, which is due to the much wea!er tendency of 86
&
to protonate
in water. 6owever, it does react with 6I to form phosphonium iodide:
& )
86 6I 86 I +
8ure phosphine ignites in air at about )&3 B, but when contaminated with traces of
8
2
6
)
it is spontaneously inflammable:
& 2 & )
86 2O 6 8O +
Illustration - ,0
H 0 O
3 4
2 : 0 C
( X )
( Y )
( t # o $ g / ;
h e a t e 1
( Z )
6 0 0 C
#I%, #J% and #H% are :
#a% 6
)
8
2
O
'
, 68O
&
and 8
)
O
1$
#b% 68O
&
, 6
)
8
2
O
'
and 8
)
O
1$
#c% 6
)
8
2
O
2
, 6
&
8O
&
and 8
)
8
2
#d% 6
)
8
2
O
2
, 68O
&
and 8
)
O
2
Page No.-9,
Ans."a$
?int : Q

2:0C 600C (t#o$g/;
3 4 4 2 6 3 4 '0
heate1
H 0O H 0 O H0O 0 O &

Illustration - ,4
6ow many 8 9 O bonds and how many lone pairs respectively are present in 8
)
O
2
moleculeG
#a% 12, ) #b% 1, 1 #c% 12, 12 #d% 12, 12
Ans. "$
?int : The structure of 8
)
O
2
is the number of 8 9 O bonds and lone pairs are shown. These are 12 and
12 respectivelyN.
< 0
0
<
0 <
0
<
< O <
O
Illustration - ,5
Chich of the following halides is most acidic G
#a% 80l
&
#b% Ab0l
&
#c% Bi0l
&
#d% 00l
)
Ans. "a$
?int : In 00l
)
carbon atom does not have d*orbitals to accommodate a lone pair of electrons and
hence is not a Dewis acid. In 80l
&
, Ab0l
&
and Bi0l
&
central atom has empty d*orbitals in each
case but electronegativity of 8 is ma"imum, hence 80l
&
is strongest acidN.
Illustration - ,3
+mong the following ions, p9 d overlap is present in
#a% 5O
&
9
#b% 8O
)
&9
#c% 0O
&
29
#d% 5O
2
9
Ans. ";$
Illustration - ,=
The compound molecular in nature in gas phase but ionic in solid state is
#a% 80l
&
#b% 00l
)
#d% 80l
3
#d% 8O0l
&
+ns. #c%
?int : Q80l
3
e"ists as Q80l
)
N
>
Q80l
2
N
9
in solid stateN.
Page No.-99
EAE!ENT% "<B(GEN @A!IA($
General p28sial properties of o:8gen famil8 elements :
Group <I#B% of the periodic table contains five elements namely o"ygen, sulphur, selenium,
tellurium and polonium. They are collectively called 2alogens or ore forming elements
because many metal ores occur as o"ides or sulphides. The first four members are non*metals,
white the last member polonium is a radioactive metal having very short half*life. +toms of the
elements have the outermost electronic configuration as
2 2 1 1
" y
ns np np np . Thus, there are two half
filled p*orbitals which are used for bonding with other elements. Aome properties of these
elements are given in the following table.
"i$ Atomi and ioni radii
+tomic #covalent% radius increases as we go down the group.
O @ A @ Ae @ Te @ 8o
Ionic Oadius of dinegative ions
2
#7 %
also increase from o"ygen to polonium. The order

is,
2 2 2 2
O A Ae Te

< < <
"ii$ Catenation
The self*lin!ing property of atoms with identical atoms is called catenation. O"ygen
shows a little tendency towards catenation, e.g., in pero"ides,
2
Q o o N

Aulphur shows a strong tendency towards catenation, e.g., in polysulphides
2
n
A

sulphanes
n
#6 A 6%,
polysulphuric acid ( )
& n &
6O A.A .AO 6
, and in various allotropes. The A * A
bond is very important in the biological systems. The A * A bonding is found in
compounds such as, cysteine, some proteins and enymes. The catenation tendency
decreases mar!edly as we go down the group
Page No.-90
"iii$ )ensit8
Kensity of group <IB elements increases in going from o"ygen to polonium, i.e., the
density of group 12 elements follows the order, O A Ae Te 8o < < < <
"i7$ !elting points and Boiling points
The melting and boiling points show regular increase with the increase in atomic number.
+s we go down the group, the molecule sie increases. +s a result <an der*CaalsS forces
increase and hence the meling and boiling points also increase.
"7$ Eletron Affinit8 7s Eletron Gain Ent2alp8
It has been recommended by IU8+0 to replace the term ,lectron +ffinity ( )
ae
,
by a new
term, ,lectron Gain ,nthalpy ( )
eg
6 .
The electron gain enthalpy is the molar enthalpy change when an isolated gaseous atom
or ion in its ground state, adds an electron to form the corresponding anion. Thus, the
enthalpy change for the reaction,
I#g% e I #g%

+
is called the electron gain enthalpy ( )
eg
6 of the element I. The
eg
6
may be positive
or negative #li!e the electron affinity%.
,lectron affinity ( )
ae
,
, or ,lectron gain enthalpy ( )
eg
6 of o"ygen and sulphur are
given below
O#g% e O #g%

+
1
ae
, #O O % 1)2!L mol

=
A#g% e A #g%

+
1
ae
, #A A % 2$$!L mol

=
2
O #g% e O #g%

+
2
ae
, #O O % '1$!L mol

= +
2
A #g% e A #g%

+
2 1
ae
, #A A % 3.$ mol

= +

Thus, the electron affinities for
2
O O

and
2
A A

are positive.
The first electron affinity of o"ygen is much smaller than those of the other elements.
,lectron affinity becomes smaller as we go down the group, i.e., from sulphur to
tellurium.
O A Ae Te 8o < > > >
Page No.-94
"7i$ Ioni&ation energ8 or ioni&ation ent2alp8, 6
The ionisation energies of group <IB elements are 4uite high. Kue to their high ioniation
energies, it is e"tremely difficult to remove electrons from the atoms of these elements.
The ionisation energy decreases as we go from o"ygen to polonium.
The first ionisation energies of lighter elements of group <IB #o"ygen family% are lower
than those of group <B, #nitrogen family%
"7ii$ <:idation states.
The outer electronic configuration of group <IB elements can be described as
2 )
ns np .
Being strongly electronegativity, these elements complete their shells by gaining two
electrons. Thus, all the elements of group 12 shows an o"idation state of *2. 6owever,
these elements also show other o"idation states as follows. O"ygen shows an o"idation
state of > 2
2
? O
in and *1 in pero"ides
2
2
O

. Other elements of group <IB e"hibit
o"idation states of > 2, > ) and > 2 also. The o"idations state of > ) and > 2 being more
stable.
?or sulphur, selenium and tellurium, the o"idation states of > ) and > 2 are important.
The > ) state is more stable for Ae, Te and 8o, then > 2 state. This is due to the
availability of d*orbitals is the valence shells of the atoms of these elements.
"7iii$ !oleular struture "or atomiit8$
O"ygen forms stable diatomic
2
O
molecules, while sulphur, selenium, tellurium and
polonium are octa atomic molecules, vi,
1 1 1
A ,Ae , Te
and
1
8o
with puc!ered*ring
structures. The puc!ered ring structure of sulphur is shown in figure. Under ordinary
conditions, o"ygen e"ists as a gas, while all other elements of this group are solids.
E:planation
This is because o"ygen has tendency to from
p p
multiple bonds. Ao, o"ygen forms
a diatomic #O P O% molecule. Kue to wea! van der CaalsS forces between the o"ygen
molecules, o"ygen e"ists as a gas.
Because of their larger atomic sie, sulphur and other heavier elements of this group do
not form stable
p p
bonds. Ao, these elements fo not occur as diatomic molecules.
Instead, A and other heavier elements of this group form 7 * 7 single bonds giving rise
to polyatomic molecule. ?or e"ample, sulphur froms ( )
1
A
octatomic molecules. Kue to
stronger van der CaalSs forces between these polyatomic molecules, these elements
#sulphur and other% e"ists as solid.
Page No.-95
Page No.-93
Page No.-9=
Page No.-9>
Illustration - ,>
In which of the following reactions O
2
is not formed as one of the product G
#a%

2
%$O
3
Heat
=C/O
#b% + +
2 3
.$C/ HC/ O
#c% + +
4 2 4 3
Fe.O H .O O #d% +
3
0*. O
Ans "$
?int : Q + + +
2 3 4 2
3.$C/ 6HC/ O 3.$C/ 3H ON
Illustration - 9-
+cidified B7nO
)
is dropped over sodium pero"ide ta!en in a flas! at room temperature, vigorous
reaction ta!es place to produce
#a% hydrogen pero"ide #b% a mi"ture of hydrogen and o"ygen
#c% a colourless gas hydrogen #d% a colourless gas dio"ygen
Ans. "d$
Page No.-0-
?int: + +
2 2 2 4 2 4 2 2
8Na O H .O Na .O H O & :
+ + + +
4 2 4 2 4 4 2
2=%$O 3H .O = .O 2%$.O 3H O :0
+ +
2 2 2 2
8H O O H O O & :
Illustration - 91
The structure of O
&
and 5
&
9
are
#a% linear and bent respectively
#b% both linear
#c% both bent
#d% bent and linear respectively
And "d$
?int :
Page No.-01
8otassium iodide and starch produces deeper blue colour with acidified
2 2
H O
2 2 3 2
H O 2H 2> > 2H O
+
+ + +
Page No.-0,
Page No.-09
C%E%
1. In bleaching of delicate materials such as sil!, wool, cotton, ivory etc.
2. +s a valuable antiseptic and germicide for washing wounds, teeth and ears under the name
perhydrol.
&. +s [antichlorS to remove traces of chlorine and hypochlorite.
). +s o"idising agent in roc!et fuels.
Illustration - 9,
+n inorganic substante liberates o"ygen on heating and turns acidic solution of BI brown and
reduces acidified B7nO
)
solution. The substance is
#a% 6gO #b% 6
2
O
2
#c% B5O
&
#d% 8b#5O
&
%
2
And ";$
?int : +
Heat
2 2 2 2
2H O 2H O O ?
+ +
"3i1i3
2 2 2
B#ow$
2=> H O 2=OH >
+cidified B7nO
)
acts as an o"idising agent when it is decolourised, 6
2
O
2
> O 6
2
O > O
2
N
Illustration - 99
Chen 6
2
O
2
is added to ice cold solution of acidified potassium dichromate in ether and the
contents are sha!en and allowed to stand
#a% a blue colour is obtained in ether due to formation of 0r
2
#AO
)
%
&
.
#b% a blue colour is obtained in ether due to formation of 0rO
3
#c% a blue colour is obtained in ether due to formation of 0rO
&
#d% chromyl chloride is formed
And ";$
?int :
+
+ + +
2
2 6 2 2 : 2
B/2e 3o/o2#
i$ ethe#
C# O 2H 4H O 2C#O :H O
Illustration - 90
Chat is false about 6
2
O
2
G
#a% acts both as o"idising and reducing agent
#b% two O6 bonds lie in the same plane
#c% plane blud li4uid
#d% can be o"idised by O
&
And "a$
Page No.-00
?int : QTwo O6 bonds lie in the different planesN
Illustration - 94
Two li4uids #+% and #B% are made of same elements and are diamagnetic. Di4uid #+% on treatment
with BI and starch gives blue coloured solution, however, li4uid #B% is neutral to litmus and does
not give any response to starch iodide paper.
Ans. Q

2 2 2
(") H O ; (B) H O
N
Sulphur
E:tration: The most important method for the e"traction of sulphur from native deposits is the
?rasch 8rocess. It consists of boring a hole from the ground surface to the sulphur bearing
calcite deposit and lowering three concentric pipes to the ore bed. Auperheated water, )&1
B, is forced down the outer pipe into the ore bed where it melts the sulphur. 0ompressed
hot air is pumped down through the innermost pipe when a frothy mi"ture of molten
sulphur, water and air is forced to the surface through the middle pipe. +s it comes out
from the well, sulphur has a purity of ...39....( and virtually does not contains +s, Ae
or Te.
Properties: Aulphur displays allotropy to a remar!able degree, e"isting both in a variety of different
molecular and physical forms. The molecular species, vi., A
2
, A
)
, A
2
and A
1
are in
e4uilibrium in gaseous sulphur, their proportions varying with the temperature. The
common and the most stable allotrope of sulphur at room temperature is !nown as
rhombic sulphur or \*sulphur,
A
. In rhombic sulpur,
1
A
rings are arranged in a way that
gives a rhombic crystal structure. +t &2. B, rhombic sulphur gets converted into
monoclinic sulphur or ]*sulphur,
A
. In monoclinic sulphur,
1
A
rings are arranged in a
monoclinic structure. It is stable between &2. and &.2 B. +t &.2 B it melts to produce a
li4uid containing A
1
molecules, A
. +t about )&& B the A

1
rings open up and Roin together
into long spiral*chain molecules resulting in a thic! viscous li4uid
*sulphur, A
. Di4uid
sulphur boils at '11 B to give gaseous sulphur containing A
1
molecules, which dissociate
to A
2
, A
)
, A
2
and finally to sulphur atoms at 22'& B. If li4uid sulphur at )2& B is poured
into cold water, plastic sulphur or *sulphur is formed. The allotropy of sulphur as a
function of temperature is summaried as follows:
&2. B &.2 B )&& B '11 B
1 2
12'& B 22'& B
) 2
A A A A A #g% A
A A A

0old water
A

Page No.-04
C<!P<CN)% <@ %CAP?C'
Page No.-05
Page No.-03
<B<ACI)% <@ %CAP?C'
The o"oacids of sulphur are more numerous and more important than those of Ae and Te. 7any of
the o"oacids of sulphur do not e"ist as free acids, but are !nown an anions and salts. +cids ending in
*ous have A in the o"idation state #>I<% and form salts ending in 9ite. +cids ending in have A in the
o"idation #>I<% state and form salts ending in 9ate
+s discussed previously under bond lengths and p 9 d bonding, the o"oanions have strong bonds
and so they have little tendency to polymerise compared with the phosphate and silicates. To
emphasie structural similarities the acids are listed in four series
1. Aulphurous acid series,
2. Aulphuric acid series,
&. Thionic acid series
). 8ero"oacid series.
Page No.-0=
Page No.-0>
Bond lengt2s and p / d ;onding
The bonds between A and O, or Ae and O, are much shorter than might be e"pected fro a single bond.
In some cases they may be formulated as localied double bonds. + 9bond is formed in the usual
way. In addition a *bond is formed by the sideways overlap of a p*orbital on the o"ygen with a d*
orbital on the sulphur, giving a p9d interaction. This p9d bonding is similar to that found in the
o"ides and o"oacids of phosphorus and is in contrast to the more common p9p type of double
bond found in ethane.
To obtain effective p * d overlap, the sie of the d*orbital must be similar to the sie of the p*
orbital. Thus sulphur forms stronger *bonds than the larger elements in the group. On crossing a
period in the periodic table, the nuclear charge is increased and more s and p*electrons are added.
Aince these s and p*electrons shield the nuclear charge incompletely, the sie of the atoms and the
sie of the d*orbitals decreases from Ai to 8 to A to 0l. The decrease in the sie of the &d*orbitals in
this series of elements leads to progressively stronger p*d bonds. Thus, in the silicates there is
hardly any p*d bonding. Thus, AiO
)
units polymerise into an enormous variety of structure lin!ed
by Ai9O9Ai 9bonds. In the phosphates, 9bonding is stronger, but a large number of polymeric
phosphates e"ist. In the o"oacids of sulphur, 9bonding is even stronger and has become a dominant
factor. Thus, only a small amount of polymeriation occurs and only a few polymeric compounds are
!nown with A9O9A lin!ages. ?or chlorine, p9d bonding is so strong that no polymeriation of
o"oanions occurs.
In cases where these is more than one *bond in the molecule it may be more appropriate to e"plain
the *bonding in terms of delocalied molecular orbitals covering several atoms.
%ulp2uri aid, "?
,
%<
0
$
7anufacture of Aulphuric +cid by 0ontact 8rocess
"i$ Prodution of %<
,
Aulphur dio"ide #AO
2
% is obtained by burning sulphur or iron pyrites

2 2
A O AO #g% +
Aulphur
2 2 2 & 2
)?eA 11O 2?e O 1AO #g% + +
Iron pyrites
"ii$ Catal8ti o:idation of %<
,
E %<
9
Aulphur dio"ide is o"idied by air in the presence of catalyst to give sulphur trio"ide.
catalyst
2 2 &
2AO #g% O #g% 2AO #g% 6 1.2.2!L +

#a% +ir or o"ygen re4uired for the o"idation of sulphur dio"ide must be in e"cess.
#b% The temperature must be low. + temperature between &3$*)3$
$
0 gives the ma"imum yield of
the product.
#c% The pressure of about 2 atmospheres is used to carry out the above reaction.
Page No.-4-
Page No.-41
Illustration - 95
Aulphur on reaction with concentrated 65O
&
gives #+% which reacts with 5aO6 gives #B%. #+% and
#B% are
#a% 6
2
AO
&
, 5a
2
A
2
O
&
#b% 5O
2
, 5a
2
A
#c% 6
2
AO
)
, 5a
2
AO
)
#d% 6
2
A
2
O
&
, 5a
2
A
2
O
&
Page No.-4,
Ans "$
?int :
+ + +
3 2 4 2 2
(")
6HNO . H .O 6NO 2H O;
+ +
2 4 2 4 2
(B)
H .O 2NaOH Na .O 2H O&
Illustration - 93
Chich of the following elements forms p*d bonding in its o"ide G
#a% Dithium #b% Boron #c% Aulphur #d% 5itrogen
Ans. "$
?int : Q+mong the given elements, sulphur forms d*p bonding in its o"ides such as AO
2
and AO
&
N
Illustration - 9=
0ompounds + and B are treated with dilute 60l respectively. The gases liberated are J and H
respectively. J turns acidified B
2
0r
2
O
'
paper green while H turns lead acetate paper blac!. The
compounds + and B are respectively.
#a% 5a
2
A and 5a
2
AO
&
#b% 5a
2
AO
&
and 5a
2
A
#c% 5a0l and 5a
2
0O
&
#d% 5a
2
AO
&
and 5a
2
AO
)
Ans. ";$
?int : QAO
2
turns acidified B
2
0r
2
O
'
paper green.
+ + +
2 3 2 4 2 4 2 2
(Y)
Na .O H .O Na .O .O H O
+ + + +
2 2 6 2 4 2 2 4 3 2 4 2
@#ee$
= C# O H .O 3.O C# (.O ) = .O H O
6
2
A turnes lead acetate paper blac!
+ +
2 2 4 2 4 2
(Z)
Na . H .O Na .O H .
+ +
2 3 2 3
H . 0* (CH COO) 0*. 2CH COOH&
Page No.-49
EAE!ENT% "?AA<GEN @A!IA($
?luorine #?%, chlorine #0l%, Bromine #Br%, Iodine #I% and +statine #+t% are grouped together to
form group 1' of the periodic table. Their salts are present in seawater and hence they are also
!nown as halogens #6alos, in Gree!, means sea salt producers%. The group collectively is called
halogen family.
The general electronic configuration of halogens is
2 3
ns np . They are Rust one electron short of
stable electronic configuration of inert gas elements. They have a very strong tendency to ac4uire
stable configuration by accepting one electron. ?or this reason they e"hibit non*metallic
behaviour. +statine, the last member of this group is a radioactive element with very short half*
life.
GENE'AA T'EN)% IN P?(%ICAA P'<PE'TIE%
Aome of the properties, of the elements of this group are given in the following table:
"i$ !elting and ;oiling points
7elting and boiling points increase with the increase in atomic number. The enthalpy of fusion
as well as enthalpy of vaporisation also increases as we go down the group. This indicates that
the strength of intermolecular forces of attraction between the molecules increases with increase
in atomic number.
"ii$ Atomi and ioni radii
+tomic radii of the elements of this group are the smallest in their respective periods. Both the
atomic radii and ionic radii for the anion
I
increase, regularly down the group because the

electrons are added to higher and higher shells.
"iii$ Ionisation energies
Ionisation energies of the all the halogens are very high. Therefore, they have very little tendency
to loose electron. 6owever, this tendency increases down the group because the nuclear force of
attraction on valence electrons decreases. Iodine is capable of forming stable compounds in
which it e"ists as
I
+
ion.
"i7$ P28sial state
Page No.-40
+ll the halogens are diatomic and e"ist as
2 2 2 2
? , 0l , Br and I
. The intermolecular forces are very
wea! and their magnitude increases down the group. Thus,
2 2
? , 0l
are gases, bromine is a
volatile li4uid and iodine is a volatile solid.
"7$ Colour
6alogens are coloured. The colour of the halogen is due to absorption of certain wavelengths of
visible light by their molecules resulting is the e"citation of outer electron to higher energy
orbitals. ?luorine being smaller in sie absorbs shorter wavelengths corresponding to violet
colour for e"citation and appears pale yellow. Iodine on the other hand absorbs longer
wavelengths corresponding to yellow colour for e"citation and therefore appears violet. In
between fluorine and iodine, the colour of chlorine is greenish yellow and of bromine is reddish
brown. Thus, the colour deepens down the group.
"7i$ Non-metalli 2arater
+ll the halogens are non*metals because of their very high ionisation energies. The non*metallic
character, however, decreases with the increase in atomic number. Iodine shows some of the
distinct metallic properties, e.g., it possesses metallic lustre and forms positive ions li!e
&
I , I
+ +
etc.
"7ii$ Eletron affinities
The halogens have strong tendency to accept electrons. Their electron affinities are highest in
their respective periods. On moving down the group the electron affinity values generally
decrease with the increase in sie of the atom. The e"ception to this general rule is fluorine which
has lower electron affinity than chlorine. It is due to the small sie of fluorine atom, the incoming
electron e"periences repulsion due to e"isting electrons in the 2p subshell resulting in low value
of electron affinity.
"7iii$ <:idation states
The most common o"idation state of all the halogens is 91, as they attain stable configuration by
accepting one electron. In fact this is the only o"idation state shown by fluorine because it is the
most electronegative element !nown. Other elements of this group also show o"idation states of
>1, >&, >3 and >'. 6igher o"idation states of these elements are due to the presence of vacant
orbitals.
,lement ? 0l Br I
+tomic 5umber . 1' &3 3&
+tomic 7ass 1. &3.)3 '...$ 122..$
,lectronic configuration
[ ]
2 3
6e 2s 2p
[ ]
2 3
5e &s &p
[ ]
1$ 2 3
+r &d )s )p
[ ]
1$ 2 3
Br )d 3s 3p
0ovalent Oadius E pm 2) .. 11) 1&&
Ionic Oadius
I
Epm
1&& 11) 1.2 22$
Ioniation enthalpyE ( )
1
!L mol
121$ 1232 11)2 1$$1

,lectron gain enthalpyE ( )
1
!L mol
9&&& 9&). 9&23 92.2

Kistance I*IEpm 1)& 1.. 22. 222
,nthalpy of dissociation
( )
1
2
I E !L mol
131.1 2)2.2 1.2.1 131.1

,lectronegativity ) &.2 &.$ 2.'
7elting point E B 3).) 1'2 223.1 &12.2
Boiling point E B 1).. 2&..$ &&2.3 )31.2
Page No.-44
Atandard Oeduction potential #AO8%
2
I 2e 2I

+
o o
2 2
? 2e 2? 2.1'< F 0l 2e 20l 1.&2<

+ = + + = +
o o
2 2
Br 2e 2Br 1.$.< F I 2e 2I $.3)<

+ = + + = +
7ore the value of the AO8, more powerful is the o"idising agent. 6ence the order of o"idising power is
2 2 2 2
? 0l Br I > > >
Aince AO8 is the highest for
2
?
#among all elements of periodic table%, it is a strongest o"idising agent.
6ydration energy of
I
Amaller the ion, higher is the hydration energy

?
0l
Br
313 &11 &)' &$3 in !LEmol

Anomalous ;e2a7iour of fluorine
The anomalous behviour of fluorine is due to its small sie, highest electronegativity, low ? 9 ?
bond dissociation enthalpy, and non availability of d orbitals in valence shell. 7ost of the
reactions of fluorine are e"othermic #due to the small and strong bond formed by it with other
elements%. It forms only one o"oacid while other halogens form a number of o"oacids. 6ydrogen
fluoride is li4uid #b.p. 2.& B% due to strong hydrogen bonding. Other hydrogen halides are gases.
"i$ 'eati7it8 to.ards 28drogen :
They all react with hydrogen to give hydrogen halides but affinity for hydrogen decreases from
fluorine to iodine with increasing atomic number. They dissolve in water to form hydrohalic
acids. The acidic strength of these acids increases in the order : 6? @ 60l @ 6Br @ 6I. The
stability of these halides decreases down the group due to decrease in bond #6 9 I% dissociation
enthalpy in the order : 6 9 ? ^ 6 9 0l ^ 6 9 Br ^ 6 9 I.
"ii$ 'eati7it8 to.ards o:8gen :
6alogens form many o"ides with o"ygen but most of them are unstable. ?luorine forms two
o"ides
2
O?
and
2 2
O ?
. 6owever, only
2
O?
is the thermally stable at 2.1B. These o"ide are
essentially o"ygen fluorides because of the higher electronegativity of flurorine than o"ygen.
Both are strong fluorinating agents.
2 2
O ?
o"idies plutonium to
2
8u?
and the reaction is used in
removing plutonium as
2
8u?
from spent nuclear fuel. 0hlorine, bromine and iodine form o"ides
in which the o"idation states of these halogen vary from >1 to >'. + combination of !inetic and
thermodynamic factors lead to the generally decreasing order of stability of o"ides formed by
halogens, I ^ 0l ^ Br. The higher o"ides of halogens tend to be more stable than the lower ones.
Halogens
a) Fluorine
E:tration: ?luorine the only practicable method of preparing fluorine gas is 7oissanSs
original procedure based on the electrolysis of B? dissolved in anhydrous 6?.
6e electrolysed a cooled solution of B? in anhydrous li4uid 6? at 23$ B using
platinum*iridium electrodes sealed with fluorspar caps in a platinum U*tube. In
this reaction, the actual electrolyte is B? while 6? acts as an ioniing solvent, ?
2
is evolved at the anode and 6
2
at the cathode as indicated below:
9
B? B ?
+
+

At the anode
9
? ? e +
Page No.-45
2
? ? ? +
At the cathode
B e B
+
+
2
2B 26? 2B? 6 + +
7oissonSs original method has been modified. In place of the e"pensive 8tEIr
alloy, cells made of copper, steel or 7onel metal, which is a nic!el*copper alloy,
have been used. +node is a carbon rod impregnated with copper to render it inert
and cathode is made of steel or copper. + mi"ture of B? and 6? in the molar ratio
of 1 : 1 or 1 : 2 is used as electrolyte.
Properties of @luorine: 8ale greenish yellow gas, which is highly poisonous and having pungent
odour. It is heavier than air. ,lectronegativity value is ).$ #8aulingSs scale%.
C2emial:
2 2 &
&6 O &? 26? O + +
2 2 2
26 O 2? )6? O + +
2 &
2+l &? 2+l? +
0opper does not appreciably react with ?
2
at this temperature because of 0u?
2
layer formation on it.
2 2 2
5aO6 2? 5a? O 26 O + + +
2 2 2
25aO6 2? ? O 25a? 6 O + + +
2 2 3
I 3? 2I? +
2 2
&? )6Br )6? Br 2Br? + + +
2 2
&? )6I )6? I 2I? + + +
2 2 ) 2
AiO 2? Ai? O + +
Atrongest o"idising behaviour of ?
2
& 2 2 )
B0lO ? 6 O 26? B0lO + + +
2 & 2 2 2 )
B 0O ? 6 O 26? B 0O + + +
2 ) 2 2 2 1
B AO ? B A O 2B? + +
C?A<'INE ( )
2
0l
P'EPA'ATI<N
#i% By heating chloride with concentrated
2 )
6 AO
in presence of
2
7nO
2
2 2 2
)6 7nO 2I I 7n 26 O
+ +
+ + + +
Bromides and iodides also liberate
2 2
Br and I
respectively with concentrated
2 ) 2
6 AO and 7nO
.
#ii% #a%
& &
5a0l 65O 5a5O 60l & + +
& 2 2
& &
65O &60l 5O0l 0l 26 O
&5a0l )65O &5a5O 5O0l
+ + +
+ +
#nitrosyl chloride% >
2 2
0l 26 O + +
#b% Chen
2
0l
is used for the chlorination of hydrocarbon the byproduct is 60l. The 60l is
catalytically o"idied into
2 2
6 O _ 0l
using copper powder mi"ed with rare earth chlorides.
Page No.-43
0u powder rare earth chloride
2 2 2
)60l O 26 O 20l
+
+ +
These methods are e"clusively used only for chlorine
Properties :
#i% It is a greenishVyellow gas with pungent and suffocating odour. It is about 2V3 times
heavier than air. It can be li4uefied into greenishVyellow li4uid which boils at 2&. B. It
is soluble in water.
#ii% +t low temperature it forms a hydrate with water having formula
2 2
0l .16
which is infact
a clathrate compound.
#iii% O"idising _ bleaching properties : 0hlorine dissolves in water giving 60I and 6Od.
6ypochlorous acid #6O0I% so formed, gives nascent o"ygen which is responsible for
o"idising and bleaching properties of chlorine.
#a% Ito"idises ferrous to ferric, sulphite to sulphate, sulphur dio"ide to sulphuric acid and
iodine to iodic acid.
#b% 0hlorine o"idies both
2 2
Br and I to Br and I

respectively.
2 2
I 0l I 20l

+ +
#c% It is a powerful bleaching agent F Bleaching action is due to o"idation.
2 2
0l 6 O 260l O + +
0oloured substance
O +
colourless substance
It bleaches vegetable or organic mather in the presence of moisture. Bleaching effect of chlome is
permanent
5ote : The bleaching action of
2
AO
is temporary because it ta!es place through reduction.
Oeduced colourless material
2
O of air

coloured material.
"i7$ 'eation .it2 Na<? :
#a% ( )
2 2
25aO6 cold _ dilute 0l 5a0l 5a0lO 6 O + + +
Page No.-4=
#b% ( )
2 & 2
25aO6 hot _ concentrated &0l 35a0l 5a0lO &6 O + + +
These reactions are also given by
2 2
Br and I
#v% Oeaction with dry sla!ed lime, ( )
2
0a O6
: To give bleaching powder.
( ) ( )
2 2 2
2 2
20a O6 20l 0a O0l 0a0l 26 O + + +
Cses :
2
0l
is used
1. for bleaching woodpulp #re4uired for the manufacture of paper and rayon%. bleaching
cotton and te"tiles,
2. in the manufacture of dyes, drugs and organic compounds such as
) &
00l , 060l
, KKT,
refrigerants, etc.
&. in the e"traction of gold and platinum.
). in sterilising drin!ing water and
3. preparation of poisonous gases such as phosgene ( )
2
0O0l
tear gas ( )
& 2
00l 5O
mustard
gas ( )
2 2 2 2
0l06 06 A06 06 0l
.
B'<!INE ( )
2
Br
:
8O,8+O+TIO5:
#i% 0ommon method : ( )
2 ) 2 2 ) ) 2
25aBr &6 AO conc. 7nO Br 7nAO 25a6AO 26 O
+ + + + +
#ii% ?rom Aea*water
5a0l is main component but 5aBr is also present in some 4uantity in sea water.
2
0l
gas is
passed through sea water when vapours of bromine are evolved.
( ) ( )
2 2
2Br a4 0l 20l a4. Br

+ +
The
2
Br
is removed by a stream of air since
2
Br
is 4uite volatile. The gas is passed through a
solution of
2 &
5a 0O
when the
2
Br
is absorbed forming a mi"ture of 5aBr and 5aBrO
&
. The
solution is then acidified and distilled to give pure bromine.
2 2 & & 2
& 2 ) & 2 )
& 2 2
&Br &5a 0O 35aBr 5aBrO &0O
35aBr 5aBrO &6 AO 36Br 6BrO &5a AO
36Br 6BrO &Br &6 O
+ + +
+ + + +
+ +
Properties :
#i% Oeddish brown li4uid, fairly soluble in water. It also forms hydrate li!e
2
0l
( )
2 2
Br .16 O 0lathrate compound
#ii% Oest reactions are same as with
2
0l
I<)INE ( )
2
I
:
P'EPA'ATI<N:
#i% 0ommon method : ( )
2 ) 2 2 ) ) 2
25aI &6 AO conc. 7nO I 7nAO 25a6AO 26 O
+ + + + +
#ii% ?rom caliche or 0rude chile salt petre:
The main source of iodine is
&
5aIO
#sodium iodate% which is found in nature with
&
5a5O
#chile saltpeter%.
&
5aIO
is present in small amount. +fter crystalliation of
&
5a5O
, the mother
li4uor left contains
&
5aIO
#soluble%. To this solution
&
5a6AO
is added where upon
2
I
is
precipitated.
Page No.-4>
2
& & )
& 2 2
2IO 26AO 2I 2AO 26
3I IO 26 &I &6 O
+
+
+ + +
+ + +
"iii$ @rom sea-.eeds:
0ertain marine plants absorb and concentrate I*selectively in presence of 0l and Br

. Aea*weeds
are dried and burnt in shallow pits, ash left is called !elp. +sh on e"traction with hot water
dissolves out chlorides, carbonates, suiphates and iodides of sodium and potassium. The solution
on concentration seperates out all leaving behind iodide in the solution. Aolution is mi"ed with
2
7nO
and concentrated
2 )
6 AO
in iron retorts. Diberated iodine is condensed in series of earthen*
ware !nown as aludels.
2 2 ) ) ) 2 2
25aI 7nO &6 AO 25a6AO 7nAO I 26 O + + + + +
#iv%
) 2 ) 2 2 2 2 2
0uAO 2BI B AO 0uI F 20uI 0u I I + + +
This
2
I
gets dissolved into BI forming
&
BI
, since
&
I
ions are yellow, therefore solution develops

yellow colour.
P'<PE'TIE%:
#i% It is a dar! violet solid, undergoes sublimation, least soluble #among halogens% in water but
much more soluble in B1#a4.% due to formation of
&
BI
. It is soluble in organic solvents li!e
& )
060l , 00l
etc. to get violet solutions.
#ii% Oeaction with hypo :
( ) ( )
2 2
2 & 2 ) 2
A O thiosulphate I A O tetrathionate ions 2I

+ +
#iii% Oeaction with
&
56
:
& & 2 2 )
15I .56 35 .I 256 I + +
#iv% Oeaction with
& &
B0lO or BBrO
:
& 2 & 2 & 2 & 2
2B0lO I 2BIO 0l F 2BBrO I 2BIO Br

+ + + +
?AA<GEN ACI)%
ACI) %T'ENGT?
It is at first parado"ical that 6? is the wea!est acid in water, since 6? has a greater
electronegativity difference than the other hybrids and therefore has more ionic character.
6owever, acidic strength is the tendency of hydrated molecules to form hydrogen ions.
#hydrated% #hydrated% #hydrated%
6I 6 I
+
+
This may be represented in stages: dissociation, ioniation and hydration in an energy cycle.
The acid strength is e4ual to the sum of all the energy terms round the energy cycle
+cid strength P ?ree energy of dehydration
> ?ree energy of dissociation
> Ioniation energy of 6
>
> ,lectron affinity I
9
> ?ree energy of hydration of 6
>
and I
9
Page No.-5-
The factor, which ma!e 6? the wea!est halogen acid in water, becomes apparent if the various
thermodynamic terms are e"amined in more detail. The dissociation constant ! for the change
#hydrated% #hydrated% #hydrated%
6I 6 I
+
+
is given by the e4uation:
o
G OTln ! =
#where
$
G
is the Gibbs standard free energy, O the gas constant and T is absolute temperature%.
6owever, G depends of the change in enthalpy 6 and the change in entropy A
G P 6 9 TA
0onsider first the total enthalpy change 6 for the dissociation of
#hydrated%
6I
into
#hydrated%
6
+
and
#hydrated%
I
. The 6 values for the various halogen acids are all negative, which means that energy,
is evolved in the process, so the change in thermodynamically possible. 6owever, the value for 6?
is small compared with the values for 60l, 6Br and 6I #which are all similar in magnitude%. Thus,
6? is only slightly e"othermic in a4ueous solution whereas the other evolve a considerable amount
of heat.
The low total 6 value for 6? is the result of several factors.
1. The enthalpies of dissociation show that the 69? bond is much stronger than the 690l, 69Br
or 69I bonds. Thus, the dissociation energy of 6? is nearly twice that re4uired to dissociate 6I.
#The strength of the 6? bond is also shown by the short bond length of 1.$ -.
2. The heat of dehydration for the step
#hydrated% #gas%
6I 6I
is much higher for 6? than for the
others. This is because of the strong hydrogen which occurs in a4ueous 6? solutions.
&. The une"pectedly low value for the electron affinity of ?
9
also contributes and though the
enthalpy of hydration of ?
9
is very high, it is not enough to offset these other terms.
?()'<@AC<'IC ACI) "?@$
C2emial Properties:
0a?
2
> 6
2
AO
)
0aAO
)
> 26?
6? etches glass. The reaction is
Ai?
)
> 26? 6
2
Ai?
2
6ence 6? is stored in polythene coated bottle.
6? 6 ?
+
+
2
? 6? 6?

+
0onRugate base ?
9
bonds with 6? by 69bonding thus statistically the effective number of
molecules of 6 drops and registers acidity B
a
P '.2 1$
9)
6
2
?
2
> BO6 B6?
2
> 6
2
O
6
&
BO
&
> )6? 6B?
)
> &6
2
O
Ai?
)
> 26? 6
2
Ai?
2
B?
&
> 6? 6B?
)
Ba0l
2
> 26? Ba?
2
> 260l
?()'<C?A<'IC ACI)
Preparation of ?Cl
Atarting materials: 5a0l, concentrated 6
2
AO
)
F temperature F 13$
$
0
Oeaction: 5a0l > 6
2
AO
)
5a6AO
)
> 60l
5a0l > 5a6AO
)
5a
2
AO
)
> 60l
8urification of 60l is done by conc. 6
2
AO
)
not by 0aO or 8
2
O
3
because both of them react with
60l.
Page No.-51
Properties
8hysical propertiesF 0olourless gas with pungent smell. It is heavier than air, highly soluble in
water.
C2emial properties
2 2 2 2
7nO )60l 7n0l 0l 26 O + + +
2 2 2 2
8bO )60l 8b0l 0l 26 O + + +
2
ordinary test
2 2 ' & 2
B 0r O 1)60l 2B0l 20r0l &0l '6 O + + + +
ordinary test
) 2 2 2
2B7nO 1260l 2B0l 27n0l 3l 16 O + + + +
& &
curdy white
+g5O 60l +g0l 65O

+ +
2 & 2 2 2 &
curdywhite
6g #5O % 260l 6g 0l 265O + +
Chat happens when urea is treated with al!aline sodium hypochlorite and heated to 1$$
$
0G
?()'<B'<!IC ACI)
8reparation of 6Br
#Oed% 28 > &Br
2
28Br
&
& 2 & &
8Br &6 O &6Br 6 8O + +
Oeaction of 5aBr with 6
2
AO
)
does not give 6Br because of the following reaction.
2 ) )
5aBr 6 AO 5a6AO 6Br + +
2 ) 2 2
6 AO 6 O AO O + +
26Br > O 6
2
O > Br
2

8urification of 6Br is done by 0a0l
2
from moisture.
Properties:
6Br is colourless and having pungent odour shows the following reactions.
Hn > 26Br HnBr
2
> 6
2

5a
2
0O
&
> 26Br 25aBr > 0O
2
> 6
2
O
5a60O
&
> 6Br 5aBr > 0O
2
> 6
2
O
'edution ation
126Br > 2B7nO
)
2BBr > 27nBr
2
> 3Br
2
> 16
2
O
26Br > 6
2
AO
)
Br
2
> AO
2
> 26
2
O
B
2
0r
2
O
'
> 1)6Br 2BBr > 20rBr
&
> &Br
2
> '6
2
O
)6Br > O
2
2Br
2
26
2
O
?()'<I<)IC ACI)
Preparation of ?I
1. #Oed% 28 > &I
2
> 26
2
O 26I > 26
&
8O
&

2. 5aI > 6
2
AO
)
5a6AO
)
> 6I
26I > 6
2
AO
)
I
2
> AO
2
> 26
2
O
&. AO
2
> 26
2
O > I
2
6
2
AO
)
> 26I
6
2
AO
)
> BaI
2
BaAO
)
> 26I
C2emial properties
)6I > O
2
26
2
O > I
2
'eduing Properties
1.
) 2 ) 2 ) ) 2 2
8in! colourless
2B7nO &6 AO 1$6I B AO 27nAO 3I 16 O + + + + +
Page No.-5,
2.
2 2 ' 2 ) 2 ) 2 ) & 2 2
B 0r O 26I )6 AO B AO 0r #AO % &I '6 O + + + + +
&.
2 2 2 2
6 O 26I 26 O I + +
). 265O
&
> 26I I
2
> 26
2
O > 25O
2
3.
& 2 2
2?e0l 26I 2?e0l 260l I + + +
2.
) 2 2 2 ) 2
20uAO )6I 0u I 26 AO I + + +
'.
& 2 2 &
8b#06 0OO% 26I 8bI 206 0OO6 + +
Oeaction with BI in acid medium gives the detection test I
9
.
2BI > 26
2
AO
)
B
2
AO
)
> AO
2
> I
2
> 26
2
O
'edution Propert8 of 28drogen 2alides
The stability of hydrogen halide decreased as we move down the group. The reducing property is
in the order 6? @ 60ll @ 6Br @ 6I. The ease of o"idation of halide ion is e"pected to increase in
the order of increasing in the order of increasing sie of the halide ions ?
9
, 0l
9
, Br
9
and I
9
. The
electrode to bt removed from ?
9
is very near to nucleus and therefore it is most difficult to
remove and easy for I
9
. Therefore, 6I should be strong reducing agent
BAEAC?ING P<*)E' ( )
2 2
0aO0l .6 O
Bleaching powder is also called calcium chlorohypochlorite because it is considered as a mi"ed salt of
hydrochloric acid and hypochlorous acid.
0a#O0l%0l
8reparation
( ) ( )
o
)$ 0
2 2
2
0a O6 0l 0a O0l 0l 6 O + +
Properties
#i% It is a pale yellow powder. It has a strong smell of chlorine. It is soluble in water but a clear
solution is never formed due to the presence of impurities.
#ii% On long standing, it undergoes auto*o"idation into calcium chlorate and calcium chloride.
( )
2 & 2
2
20aO0l 0a 0lO 30a0l +
#iii%
2
0o0l
2 2 2
20aO0l 20a0l O +
#iv% In presence of a little amount of a dilute acid, it loses o"ygen.
2 2 ) 2 )
20aO0l 6 AO 0a0l 0aAO 260lO + + +
60lO 60l O +
On account of the liberation of nascent o"ygen, it shows o"idising and bleaching properties.
#a% O"idising properties
2 2 2 2
0aO0l 6 A 0a0l 6 O A + + +
2 2 2 2
0aO0l 2Bl 260l 0a0l 2B0l 6 O I + + + + +
2 & 2 2 2
&0aO0l 256 &0a0l &6 O 5 + + +
It o"idies
& & 2 &
2 & & )
5O to 5O , +sO to +sO and ?e to ?e
+ +
#b% Bleaching action
#v% Chen bleaching powder reacts with dilute acids or
2
0O
it liberates chlorine which is !nown as
available chlorine.
Page No.-59
2 2 2 2
2 2 ) ) 2 2
2 2 & 2
0aO0l 260l 0a0l 6 O 0l
0aO0l 6 AO 0aAO 6 O 0l
0aO0l 0O 0a0O 0l
+ + +
+ + +
+ +
&
65O
is a strong o"idising acid to be avoided, here
E%TI!ATI<N <@ ADAIAABAE C?A<'INE:
Det the weight of sample of bleaching powder be Cg.
+dd into a bea!er containing acetic acid solution and e"cess BI. + yellow brown solution is
formed ( ) &
I
the titrant. 5ote the volume where the blue colour disappear.
( )
+dd to bea!er +dd a drop
C gm. Jellow brown
0ontaining of Atarch
Aolution
B.8
06 0OO6 _ ,"cess BI
&

+dd Iodometric
Blue
6ypo Titration

+t end point blue colour disapper
Oeaction involved :
( )
2 & & 2 2
2
0aO0l 206 0OO6 06 0OO 0a 6 O 0l + + +
2 2
0l 2BI 2B0l I + +
2 2
2 2 & ) 2
I 2A O A O 2I

+ +
0alculation :
hypo hypo
1
7 < '1
2
(0l 1$$
C

=
#vi% Bleaching powder converts acetone or ethyl alcohol into
&
060l
( )
2 2 2
2
0aO0l 6 O 0a O6 0l + +
& & 2 & &
06 0O06 &0l 00l 0O06 &60l + +
( ) ( )
& & & &
2 2
200l 0O06 0a O6 06 0OO 0a 2060l + +
Illustration - 9>
The property of halogens, that indicated incorrect is
#a% ? ^ 0l ^ Br ^ I....... ionisation energy #b% ? ^ 0l ^ Br ^ I....... electron affinity
#c% ? ^ 0l ^ Br ^ I ...... electronegativity #d% I ^ Br ^ 0l ^ ?...... density in li4uid state
Ans. ";$
?int : QThe electron affinity of 0l is ma"imum. The trend is : 0l ^ ? ^ Br ^ IN
Illustration - 0-
C /
2
C o / 1 a $ 1 1 i / 2 t e N a O H
H o 1 a $ 1 3 o $ 3 . N a O H
( " ) ) N a C / ) H O
2
( B ) ) N a C / ) H O
2
0ompounds #+% and #B% are :
Page No.-50
#a% 5a0lO
&
, 5a0lO #b% 5aO0l
2
, 5aO0l
#c% 5a0lO
)
, 5a0lO
&
#d% 5aO0l, 5a0lO
&
Ans. "d$
?int :
+ + +
2 2
Co/1 a$1 1i/.
(")
C/ 2NaOH NaC/ NaOC/ H O
+ + +
2 3 2
Hot a$1 3o$3.
(B)
3C/ 6NaOH :NaC/ NaC/O 3H O&
Illustration - 01
The property of halogen acids, that indicated incorrect is
#a% 6? ^ 60l ^ 6Br ^ 6I.......acidic strength
#b% 6I ^ 6Br ^ 60l ^ 6?.....reducing strength
#c% 6I ^ 6Br ^ 60l ^ 6?........bond length
#d% 6? ^ 60l ^ 6Br ^ 6I......thermal stability
Ans. "a$
?int : Q6I is the strongest acid while 6? is the wea!est acid. The order of acidic strength is
6I ^ 6Br ^ 60l ^ 6?N
Illustration - 0,
The halogen that is most readily reduced is
#a% fluorine #b% chlorine #c% bromine #d% iodine
Ans. "a$
?int : QThe reduction potential of fluorine is ma"imum and thus, it is easily reduced, i.e., it acts as
strongest o"idising agentN.
Illustration - 09
" g C / O ) ( " ) ( B ) ) ( C ) ) ( + )
3

% $ O ) H C /
2
C o $ 3 .
The substances #+%, #B%, #0% and #K% are
#a% 0l
2
, +g0l, 0lO
2
, O
2
#b% 0l
2
, +g, 0l
2
O
2
, O
2
#c% 6
2
, +g0l, 6
2
O, O
2
#d% 60lO, +g0l, 0l
2
O, O
2
Page No.-54
Ans. "$
?int :
+ + +
3 2 2 2
(B) (") (C) (+)
2"gC/O C/ 2"gC/ 2C/O O &
Page No.-55
Page No.-53
Page No.-5=
P%EC)<?AA<GEN% AN) P%EC)<?AAI)E%
+ few ions are !nown, consisting of two or more atoms of which at least one is 5, that have
properties similar to those of the halide ions. They are therefore called pseudohalide ions. 8seudohalide
ions are univalent, and these form salts resembling the halide salts. ?or e"ample, the sodium salts are
soluble in water, but the silver salts are insoluble. The hydrogen compounds are acids li!e the halogen
acids 6I. Aome of the pseudohalide ions combine to form dimmers comparable with the halogen
molecules I2. These include cyanogens ( )
2
05
, thiocyanogen ( )
2
A05
and selenocyanogen ( )
2
Ae05
Anion Aid )imer
05
cyanide ion
A05
thiocyanate ion
Ae05
selenocyanate ion
O05
cyanate ion
2
505

cyanamide ion
&
5
aide ion
605 hydrogen cyanide
6A05 thiocyanic acid
6O05 cyanic acid
2
6 505
cyanamide
&
65
hydrogen aide
( )
2
05
cyanogens
( )
2
A05
thiocyanogen
( )
2
Ae05
selenocyanogen
The best !nown pseudohalide is
05
. This resembles
0l
,
Br
and
I
in the following respects.

1. It forms an acid 605
2. It can be o"idied to form a molecule cyanogens ( )
2
05
&. It forms insoluble salts with
2
+g , 8b and 6g
+ + +
). Interpseudohalogen compounds 0l05, Br05 and I05 can be formed.
3. +g05 is insoluble in water but soluble in ammonia, as is +g0l.
2. It forms a large number of comple"es similar to halide comple"es.
e.g.
( ) [ ] ( ) [ ]
& 2
2 &
) 2
2 2
0u 05 and 0u0l and 0O 05 and 0o0l

General Properties
"i$ P28sial state
The interhalogen compounds may be covalent gases #e.g. 0I?, Br?,
& '
0l? , I?
%, li4uids #e.g.
& 3
Br? , Br?
% or solids #e.g. I0l, IBr,
& &
I? , I0l
%
"ii$ Colour
+lthough many of the interhalogen compounds containing fluorine are colourless, yet those
made up of heavier halogens are coloured. The colour becomes deeper with the increase of the
molecular weight of the compound. In this behaviour these compounds resemble the halogens
themselves.
"iii$ )iamagneti nature
Aince all the valence electrons in interhalogen compounds are present as bonding or non*
bonding #i.e., lone pairs% electron pairs, these compounds are diamagnetic in nature.
"i7$ ?eats of formation
+ll these compounds have low heats of formation. ?or e"ample, these values for IBr and Br0l
are V2.3 and V$.&) !calEmole respectively. These are e"tremely volatile compounds. In general
compounds containing fluorine are more volatile than those containing chlorine, bromine or
iodine.
"7$ Boiling points
?or each type of interhalogen compounds, the boiling points increase with the increase in the
electronegativity difference between + and B atoms.
Page No.-5>
"7i$ T2ermal sta;ilit8
Thermal stability of +B type interhalogen compounds decreases with the decrease in
electronegativity difference between + and B atoms. Thus the order of stability of some +B
compounds is as
I? #1.3%^ Br? #1.2% ^ 0I? #1.$% ^ I0l #$.3% ^ IBr #$.&%^ Br0l #$.2%
In parentheses are given the electronegativity difference between + and B atoms. The above
order is also e"plained by saying that greater is the difference between the electronegativity
values of + and B, the more polar is the +9B bond and hence greater is the thermal stability of
+B compound.
"7ii$ 'eati7it8
+B type compounds are more reactive than
2
+
and
2
B
molecules, since +VB bond in +B
compounds is wea!er than +V+ and BVB bonds in
2
+
and
2
B
respectively. Thus +B type
compounds convert the metals into a mi"ture of two halides. ?or e"ample
I0l 25a 5aI 5a0l + +
The order of reactivity of some interhalogen compounds has been found as
& & ' 3
0l? Br? I? Br? Br? > > > >
.
"7iii$ ?8drol8sis
6ydrolysis gives halogen acid and o"y*halogen acid. The o"y*halogen acid is of larger
#i.e., central% halogen atom. ,"amples are
2
Br0l 6 O 60l + #halogen acid% > 6OBr #o"y*halogen acid%
2
I0l 6 O 60l 6IO + +
& 2 2
3 2 &
3 2 &
' 2 3 2
I0l 26 O &60l 6IO
I? &6 O 36? 6IO
Br? &6 O 36? 6BrO
I? 26 O '6? 6 IO
+ +
+ +
+ +
+ +
FE'< G'<CP
The elements helium #6e%, neon #5e%, argon #+r%, !rypton #Br%, "enon #Ie% and radon #On% belong to
group 11 of the periodic table. +ll these elements are gaseous under ordinary conditions of temperature
and pressure. The last member of the group i.e., radon is obtained from radioactive disintegration of
radium. +ll others are present in air in traces. They are also !nown as rare gases, because they are found
in very small amounts in nature. They are highly non*reactive and baring few e"ceptions, they donSt ta!e
part in chemical reactions and are therefore, called inert gases or noble gases. They always occur in free
state because of the inert nature.
The valence shell electronic configuration of helium is 1s
2
and for other members of this group is
2 2
ns np . Thus, e"cept helium, other noble gases have a closed octet of electrons in their outermost shell.
This electronic configuration is very stable and is related to their chemical inertness.
Their physical properties show a regular gradation. Aome of the physical properties are given in the
following table:
Page No.-3-
,lements Ionisation energy
( )
1
!L mol
Kensity at AT8
( )
&
g cm
7elting point
#B%
Boiling point
#B%
6elium 2&'&
)
1.1 1$
V ).2
5eon 2$1$
)
..$ 1$
2).2 2'.1
+rgon 132$
&
1.1 1$
1&.1 1'.2
Brypton 1&31
&
&.' 1$
113.. 11..'
Ienon 11'$
&
3.. 1$
121.& 123.$
Oadon 1$&'
&
..' 1$
2$2 211
GENE'AA T'EN)% IN P?(%ICAA P'<PE'TIE%
"i$ %tate
+ll of them are monoatomic, colourless, odourless and tasteless gases.
"ii$ %olu;ilit8
They are sparingly soluble in water. The solubility generally increases with increase in atomic
number.
"iii$ Boiling point and melting point
Kue to wea! intermolecular van der CaalSs forces between them they possess very low boiling
point and melting point in comparison to those of other substances of comparable atomic and
molecular masses. 6owever, the boiling point and melting point increase with increase in atomic
number because van der CaalSs forces become stronger with increase in sie of the atoms or
molecules. Therefore, among noble gases radon has the highest melting point and boiling point
whereas helium has the least melting point and boiling point.
"i7$ AiGuefiation
It is e"tremely difficult to li4uefy these gases as there are only wea! van der CaalSs forces which
hold atoms together. Aince these forces increase with the increase in atomic sie and population
of electrons, ease of li4uefication increases down the group from 6e to On.
"7$ Atomi radii
In the case of noble gases, the atomic radii corresponds to van der CaalSs radii. Therefore, these
are 4uite large as compared with atomic radii of the other atoms belonging to the same period. +s
we go down the group, the van der CaalSs radius increases due to the addition of new electronic
shells and increase in screening effect.
"7i$ Ionisation energies
The ionisation energies of noble gases are very high. This is due to the stable configurations of
noble gases. 6owever, the ionisation energies decrease with increase in atomic number from 6e
to On due to increasing atomic sie and decrease in effective nuclear charge.
"7ii$ Eletron affinities
Kue to the stable
2 2
ns np electronic configurations, noble gas atoms have no tendency to accept
additional electron. Therefore, their electron affinities are almost ero.
"7iii$ Ent2alp8 of fusion and ent2alp8 of 7apouri&ation
In general, the enthalpies of fusion and the enthalpies of vaporiation are low and increase down
the group.
Page No.-31
Page No.-3,

Page No.-39
Illustration - 00
Chat are the products formed in the reaction of "enon he"afluoride with silica G
#a% IeAiO
)
> 6? #b% Ie?
2
> Ai?
)
#c% IeO?
)
> Ai?
)
#d% IeO
&
> Ai?
)
Ans. "$
?int : Q + +
6 2 4 4
2XeF .iO 2XeOF .iF &
Illustration - 04
Chich of the following two are isostructural G
#a% Ie?
2
, I?
2
9
#b% 56
&
, B?
&
#c% 0O
&
29
, AO
&
29
#d% 80l
3
, I0l
3
Ans. "a$
?int : QIe?
2
is a linear molecule #Ie and sp
&
d hybridied with three e4uatorial positions occupied by
line pairs%.
I?
2
9
is a linear molecule #I is sp
&
d hyhrbdied, with three positions occupied by line pairs%,N
Illustration - 05
Ie?
2
reacts with Ab?
3
to form
#a% QIe?N QAb?
2
N #b% QIe?
&
N QAb?
)
N #c% IeO
&
#d% Ie?
&
Ans "a$


Preparation and Properties of Compounds

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Preparation and Properties of Compounds

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Page No.

I 1)$2 1$12 .)' 1&) '$&

9 )2.1 1&.) 22.) 1)3.1 2'1

also increase from o"ygen to polonium. The order

. +t about )&& B the A

increase, regularly down the group because the

121$ 1232 11)2 1$$1

9&&& 9&). 9&23 92.2

131.1 2)2.2 1.2.1 131.1

Amaller the ion, higher is the hydration energy

313 &11 &)' &$3 in !LEmol

ions are yellow, therefore solution develops

in the following respects.

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