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 p-Block Elements
 Elements having its last electron in p-subshell is called p-block elements.
 ‘He’ has its last electron in its s-subshell but it is a p-block elements.
p-block element starts from group 13 and ends with inert gas element of group 18.

GROUP - 13 (BORON FAMILY)

Element Atomic number Outer electronic configuration
B 5 2s2 2p1
Al 13 3s2 3p1
Ga 31 4s2 4p1
Ia 49 5s2 5p1
Tl 81 6s2 6p1

GENERAL PROPERTY
1. Atomic Radius : B < Ga < Al < In < Tl
The atomic radius of ‘Ga’ is found to be exceptionaly less than that of Al. due to the poor screening of d-
electrons in Ga.
2. Metallic Character : Boron is a typical non-metal but Al is metal.
AlGa  In  Tl
3. Oxidation - states : 
Stability of 1stateincreases

4. Hydrides :
Hydrides

Nido-Boranes Arachano-borane
Bn Hn+4 Bn Hn+4
of all the hydride the diborane (B2H6) is most important
(a) 4BF3 + 3LiAlH4 
 2B2H6 + 2NaI
(b) 2NaBH4 + I2  B2H6 + 2NaI

(c) BF3 + 6NaOH 
450 K
 B2H6 + 6Na F

PROPERTY OF DIBORANE

(i) Combustion:
B2 H6  3O2 
 B2 O3  3H 2 O H  1976 kJmol1
(ii) Hydrolysis :
B2 H6 (g)  6H 2 O(l ) 
 2B(OH)3  6H 2 (g)
(iii) Reaction with Ammonia :

 3 BH 2 (NH 3 ) 2   BH 4 
B2 H 6  6NH 3 

2B3 N 3 H 6  12H 2
Borazine
(Inorganic benzene)

[1]
 Structure of inorganic benzene :

H H

B +
B
+
H–N N–H H–N N–H

H–B B–H H–B B–H

N N+ Borazine
H Borozine H

Structure of diborane :
H H H

B 970 B 1200

H H H
 The four terminal H and two borons are in one plane.
 Above and below this plane, there are two bridging H.
 The 4 terminal B–H bonds are regular 2C–2e bond while the two bridge H are 3C-2e bonds.
(b) Halides :

M  3X2 
 MX3
 Tl(11I) iodides are not known to exists.
Structure of AlCl3 : AlCl3 exists in its dimeric state.
Cl Cl Cl

Al Al

Cl Cl Cl
In polar solvent like H2O, the covalent dimers dissociate into [Al (H2O)6]3+ due to high heat of hydration.
3
 2  Al(H 2 O)6   6Cl (aq)
Al2 Cl6  12H 2 O 
sp3 d 2

 White fumes are observed over the bottles of anhydrous AlCl3. This is due to the partial hydrolysis of
it in presence of moisture to liberate HCl(gas) which appears white.
 All group 13 element except B shows higher oxidation state. Boron does not shows because of non-
avalibility of vacant ‘d’ orbitals.
Reactivity towards air :

(a) 2M(s)  3O2 (g) 

 2M 2 O3 (s)
B2 O 3 , Al2O3 , Ga 2O3 , In 2O3 , Tl2O
Acidic
1442443 14 4244 3

Amphoteric Basic
Basic character increases


(b) 2M  N2 (g) 
 2MN(s)
Reactivity towards Acids :

 2Al3  6Cl (aq.)  3H2 (g)

2 Al(s)  6HCl(aq) 
 But concentrated HNO3 renders (Al) passive by forming a protective oxide-layer on surface.
Reactivity with Base :

2Al(s)  2NaOH(aq)  6H 2 O(l )  2Na   Al(OH) 4   aq   3H 2 (g)
Sod. tetrahydroxo aluminate (III)

BORAX
(Na2B4O7. 10H2O)
2
Borax has tetranuclear units and in reality it exists as  B4 O5 (OH) 4  with correct molecular formula as

Na 2  B4 O5 (OH) 4 

1. EFFECT OF HEAT ON BOROX :


Na 2 B4 O 7 . 10H 2 O   Na 2 B4 O7  2NaBO 2  B2 O3
(Boricanhydride)
Borax bead test : On heating borax it 1st loses water to swell up. On further heating it forms transparent
liquid, which later solidifies into glass like material called as borax-bead. The meta borates of several transition
metal has its own characteristic colour which is used to identify them in laboratory.
e.g. When Borax is heated in Bunshen flame with CoO, a blue colour of CO(BO2)2 bead is formed.

2. DISSOLUTION IN ALKALI :

Na 2 B4 O 7  7H 2 O 
 2NaOH  4H 3 BO3
ortho boric acid

BORIC ACID
PREPARATION :

Na 2 B4 O 7  2HCl  5H 2 O 
 2NaCl  4B(OH)3
Boricacid

PROPERTIES :
(i) Sparingly soluble in normal water but soluble is hot water.
(ii) Boric acid is a weak mono basic acid. It is not a protonic acid but acts as Lewis acid.

  B(OH) 4   H3 O 
B(OH)3  2H 2 O 
(iii) Action of heat
  
H3 BO3   H3 BO2   B2 O3

Structure of Boric Acid :

H
O

H B H
O O

H H

O O
B
O
H

GROUP 16

Carbon Silicon Germanium Tin Lead

 C Si Ge Sn Pb
Among all these elements, Si is the 2nd most abundant on earth and exist widely as Silicate and clay.

GENERAL PROPERTY :

1. Oxidation - state :
Carbon : Carbon in general forms covalent compounds having oxidation state of +4. But in few carbides
carbon has ionic oxidation state as well as C4–.
e.g. Be 2 C, CaC 2 , SiC, Al4 C 3

2. Higher oxidation state:

Except carbon all other elements forms compound of higher co-ordination number of 5 and 6.
e.g. SiF5 , SiF62  , PbCl26  etc.
Ge Sn  Pb

Stability of divalent state

Note : SiF62  exists but SiCl26  do not exists. This is since, smaller size of F will cause less amount of steric
repulsion in it while due to the compartively larger size of Cl, there will be high steric repulsion. In addition,
the interaction of l-p of electron in F will be more with silicon than with Cl.
3. Catenation :

C Si  Ge Sn  Pb

Tendency of catenation increases


4. p  p multiple bonds :
Due to small size and high concentration carbon has very strong tendency to form p  p multiple bond
 with itself, O, and N,
e.g. C = C, C  C ,  C  O, CN
 other element of this group is reluctant to form p  p bond.

5. p  d bonding :

Carbon do not forms p  d bond, because it don’t have d orbital available. However Si and other elements
of this group forms p  d bond.
 N(CH3)3 is pyramidal whereas N(SiH3)3 is planar..
SiH3 SiH3

N
N
CH3 CH3
CH3
Pyramidal ( sp3) SiH3
planar (sp2)
Allotropy: All the elements of this group except lead, shows allotropy.

ALLOTROPIC FORM OF CARBON :

(i) Amorphous (ii) Crystalline
 Diamond and Graphites are the two crystalline forms .
1. Diamond :

 It has crystalline lattice.

 It has sp3 hybridization of carbon to which other carbons are arranged tetrahedrally.
 The crystalline structure extends in space and produces rigidity in 3D structural form. The bonds are directional
in nature.
2. Graphite :
Graphite has layer like structure in which layers are held together by vander waal forces.Each layer is
composed of hexagonal rings of carbon with sp2 hybridized state.
3. Fullerene :
It was discovered by H.W.kroto, E.smalley. R.F. curl in 1985. For this they were awarded with Nobel prize
in 1996.
Preparation :
Heating of Graphite in an electric arc in the presence of inert gas such as the argon. Fullerene are the purest
form of allotropes of carbon.
Structure :
C60 molecule has a shape like soccer ball and is called Buckminister fullerenes. It has 20 six membered rings
and 12 five membered rings. All the carbon atoms are equal and undergoes sp2 hybridization.
Fullerene molecule has aromatic character because of its delocalised electron. Spherical fullerenes are also
called Bucky balls.
Chemical :
(1) Oxides :
(a) Monoxide : All elements except silicon has monoxide.
CO , GeO , SnO, PbO
 neutral acidic amphoteric alkaline
 CO is colourless poisonous gas.
CO2 , SiO 2 ,GeO 2 ,SnO 2 PbO 2
(b) Dioxide : {Gas
1444 424444 3
Solid

Si O Si O Si

O O O

Si O Si O Si O

Giant network structure of SiO2

(2) Silicones :
The synthetic material containing Si–O–Si linkage are called silicones. These are polymer having
R2SiO as repeating units.

R R R
| | |
H 2O
R 2SiCl 2   O  Si  O  Si  O  Si  O 
| | |
R R R

GROUP - 15

The elements of this group is called Pniconides. The word is derived from greek word ‘Pniconides’ which
means ‘Suffocation’.
(1) Oxidation state :
Only nitrogen forms few ionic compound in N3– state, while all other elements gives rise to covalent compounds.
 Few ionic compounds of nitrogen - Mg3N2, Ca3N2 etc.
 Since nitrogen do not have vacant d-orbital so it can’t extend its covalency in excess of 4 e.g.
NH 4 ,R 4 M  etc.
 On the otherhand other elements of this group exhibit higher covalency of five or even six eg. PCl5,
AsF5, PF6 , SbF6

(2) Metallic Character:

N, P As, Sb Bi
{ , 123 {
Non  metal Metalloid Metal

(3) Nature of Bonding :

Due to smaller size nitrogen forms p  p multiple bonding with itself and with carbon and oxygen.
.. ..
 N  N , Due to the triple bond N2 has very high bond dissosiation energy and it becomes inert and
unreactive.
 No other element of this group forms p  p multiple bonding. This is due to why nitrogen exists at N2,
whereas phosphorus exist as P4.
ALLOTROPES OF PHOSPHORUS :
Three allotropes
(i) White phosphorus (ii) Red phosphorus (iii) Black phosphorus
1. White phosphorus :
(a) It exists as P4 units. The four phosphorus atoms lie at the corner of a regular tetrahedron
with PPP  600 .
P

P P

P
White Phosphorus
(b) On exposure to light, white phosphorus turns yellow. Thus it is also called yellow phosphorus. It is highly
toxic.
(c) It is very reactive and spontaneously catches fire in air with greenish glow.
P4  3O2 
 P4 O6
2. Red phosphorus :
(a) When white phosphorus is heated to 570 K in an inert atmosphere for several days, it gets
converted into red phosphorus.
(b) Red phosphorus has higher m.pt than white phosphorus.
(c) Red phosphorus is amorphous and has a polymeric structure.
P P P

P P P P P P P

P P P
Polymeric Strucutre of Red Phosphorus
(d) It is much less reactive than white phosphorus and is non-toxic.
3. Black phosphorus :
Thermodynamically the most stable form of phosphorus is black phosphorus
(a) It is obtained by heating white phosphorus at 470 k under high presure.
4. Hydrides :
All elements of this group forms gaseous hydride of MH3 type.
NH3, PH3, AsH3, SbH3, BiH3.

Stability of hydrides decreases

Few reactions given by Hydrides:
1. Ca3P3 + 6H2O 
 2PH3 + 3Ca(OH)2
 2. P4  3K  OH  3H 2 O 
 PH 3  3KH 2 PO 2
3.  2MH3  3ZnCl2 (aq) M = As or Sb.
Zn3 M 2 (s)  6HCl(aq) 

Boiling point :

BiH3 SbH3  NH3  AsH3  PH3

 B.Pt.

From PH3 to BiH3 there is increases in B.pt. due to the increase in surface area.
 But NH3 has exceptionaly large B.Pt. due to extensive H-bonding in it.
Basic Character :
NH 3  PH 3  AsH 3 SbH 3  BiH 3

Basic character increase

Structure :
It has pyramidal structure

H H H
Halides :
Two halides in general (a) MX3 (b) MX5
MX3
PF3/ PCl3 : It is pyramidal in gaseous state.

P
96.30
F F
F
Properties : MX3 fumes in moist air because of its rection with H2O producing HCl.
PCl3  3H2 O 
 3H3 PO3  3H  Cl
CCl4
MX5 : PCl3  Cl2   PCl5
PF5 is molecular in both gaseous and solid states and has ‘Trigonal bipyramidal’ structure.

 PCl5 fumes in air. It reacts with H2O to give initially POCl3 but with excess of H2O, the product is H3PO4
PCl5  H 2 O 
 POCl3  2HCl

POCl3  3H 2 O 
 H3 PO 4  3H  Cl
 
PCl5 in gaseous and liquid phase is molecular while in solid phase it is ionic and exists as  PCl 4   PCl 6  .

OXIDES
Two types of oxides - (a) M2O3 (b) M2O5
 Due to the formation of multiple bonding they have cage structure.
 The basic nature of these oxides increases with increase in atomic number. Because of its great
affinity with water, P4O10 is used as dehydrating agent.
 P4 O6  6H 2 O 
 4H3 PO3

P4 O10  6H2 O 
 4H3 PO3
P2 O 3 , AS2 O3 , Sb 2O 3 , Bi 2 O3
144244 3 123 123
Acidic Amphoteric Basic

Basic strength increases

Structure of P4O6 :

O O
O

P P

O P
O

Structure of P4O10 :
O
P

O O
O

O P P O

O P
O O

NITRIC ACID (HNO3):

It is manufactured by contact process to use following reactions.
Pt / Rh
4NH 3  5O 2 (g) 
Catalyst
4NO(g)  6H 2 O(g)
1120K
2NO  O2 (g)   2NO2 (g)

3NO2 (g)  H 2 O(l ) 

 2HNO3  NO(g)

Nitrate ion Test :

H  NO3  3Fe2  
 NO  3Fe3  2H 2 O
2 2
 Fe(H2O)6    Fe(H 2 O)5 NO  H 2 O
 NO 
Brown ring
Oxo-Acids of Phosphorus :

O O O
P P P

H O O H H O O O H
O H OH OH
Ortho-phosphoric acid Pyrophosphoric Acid

O O

P P

H O H O H H H O H

Phosphorous Acid Hypophosphorus Acid

GROUP - 16

 They are called chalcogens, i.e. ore producers.

O, S, Se, Te, Po
 Polonium is radioactive.
General Configuration : ns2 np4 .

ALLOTROPES :
Sulphur forms numerous allotropes in which its two common allotropes are
(i) Yellow ortho rhombic (ii)  ,   monoclinic
 The stable form at room temperature is orthorhombic sulphur, which transforms to monoclinic sulphur
at 369 K.
S8 molecules are puckered up to give different crystal structure in two forms. The S8 ring in the two
form is puckered and gives crown ring structure.

S
S S S
S
S
S S
S S
S
S S
S

(a) S8 (b) S6
 Few other Allotropic modification of sulphur containing upto 20 sulphur atom per ring have been
synthesised.
 The ring takes chair form in S6.
Catena (Sn) :
Chain polymeric allotropes of sulphur is called catena. They have the general formual of Sn where
n = 2 to 5. They exists as liquid sulphur at higher temperature. At 1000 K S2 is the most dominant species
and S2 is paramagnetic.
Oxidation state :
The important common oxidation states for group 16 elements are –2, +4, +2, +6 oxygen due to non availability
of vacant d orbital does not shows higher oxidation states.
Metallic Character :
Except Po* all other elements of this group is non metal. Metallic character increases down the group.
Hydrides :
Type H2X.
H2O, H2S, H2Se, H2Te, H2PO*
Thermal stability decreases
 
Band dissosiation energy decreases
  
acidic character increases
 
 B.Pt. H2O > H2Te > H2Se > H2S

Halides :

SF4 SCl 4  IBr4 SI 4


stability increases

Preparation:
1
(a) S8  3F2 (g) 
 SF6
8
1
(b) S8  Cl2 (g) 
 S2 Cl2
4
 SF6 is inert, nontoxic gas. The inertness of SF6 is due to the sterically protected sulphur atom which does not
allow thermodynamically favourable reaction to take place. Due to this it rarely undergoes hydrolysis.
 But SeF6 and SF4 which is less sterically hindered undergoes hydrolysis.
 Because of the inertness of SF6 and good dielectric property it is used as gaseous insulators.
Structures
a) SF4: ‘S’ has sp3d hybridization in SF4 b) SF6 : ‘S’ has sp3d2 hybridization SF6
Octahedral
F

F F F
F
F S
S
F
F F
F (SF4)
F (SF6)
 SeCl4, SeBr4, TeB4 and TeI4 exists as tetramer while TeF4 has polymer structure.
Oxides
General formula is EO2 and EO3. SO2 is gas at room temperature and has an angular structure with bond angle
119°. It exists as discrete SO2 molecule in gaseous state but SeO2 in solid state has a layer structure. SO3 in gas
phase exists as planar triangular structure. In solid state SO3 exists as linear cyclic trimeric or a polymeric chain.
Oxoacids of Sulphur
1. H2SO3 (Sulpurous acid)
2. H2SO4 (Sulphuric acid)
3. H2S2O7 (Pyrosulphuric acid or oleum)
4. H2SO5 (Peroxomonosulphuric acid or caro’s acid)
5. H2S2O8 (Peroxodisulphuric acid or Marashall’s acid)
6. H2S2O3 (Thiosulphuric acid)
7. H2S2O6 (Dithionic acid)

GROUP - 17 HALOGENS

Halo means salt producing. Most reactive non-metals are F, Cl, Br, I but At is radioactive.

ATOMIC AND PHYSICAL PROPERTIES:

Exists as diatomic molecules under ordinary condition.

I2
F2 , Cl 2 Br2 Lustrous,
Pale yellow Brown
E555F grayish black
and greenish yellow crystalline
 Sparingly
solublein solid sublimes
react with to form deep
H 2O H 2 O but
solublein violet vapours
organic
solvents
F–F bond energy is smaller than Cl–Cl but X–X bond energy after Cl2 decrease due to increased size of X
and less effective overlapping of atomic orbitals. F–F bond is weaker than Cl–Cl due to small size and large
electron-electron repulsion of the lone pairs in F2.

OXIDATION STATE AND TRENDS IS CHEMICAL REACTIVITY :

F is the most electronegative its oxidation state is –I in all compounds and is the strongest oxidising agent.
X2 + 2e–  2X– (accepts electrons : all are good oxidising agent).
 Oxidizing power decreases down the group. Any halogen of lower atomic number can oxidize the
halide ion of higher atomic number.
F2 + 2X–  2F– + X2 (X = Cl, Br or I)
Cl2 + 2X–  2Cl– + X2 (X = Br or I)
Br2 + 2I–  2Br– + I2
 Interhalogen are compounds with formula AXn where halogens combine among themselves. A and X
both are halogens but X is more electronegative than A.
Hydrogen Halides : HX are Covalent molecular species. HX in aqueous form are called hydrohalic acids.
  Acidic character in aqueous solution.
HF < HCl < HBr < HI
 HF is a much weaker acid (Hydrogen bonding and high bond dissociation energy of H–F bond).
 HF is corrosive and attacks glass, therefore used in etching of glass and manufacture of glass shells of
T.V. tubes.
 Oxides OF2 and O2F2 called oxygen fluorides. Because F is more electronegative.
Oxoacids:
HOCl < HOClO2 < HOClO3 < HOClO4

acidic strength increases

Inter-halogen compounds AX n:
n = (1, 3, 5 or 7)
e.g. AX AX3 AX5 AX7
ClF ClF3 ClF5 IF7
BrF BrF3 BrF5 IF7
ICI IF3 IF5

 Stability of inter-halogen compound increases as the size of the central atom increases. The more
electronegative halogen is given a –ve oxidation state.
 They are strong oxidising agents and covalent. AX3 have T-shape structure. AX5 have square
pyramidal. ClF3 is used as a fluorinating agent.
U(s) + 3ClF3  UF6(g) + 3ClF(g)
Polyhalide anions :
XYn (n = 1, 2, 3, 4)

e.g.: I3  linear triatomic iodide ion

Polyhalonium cations:
They are XY2n type

e.g. CIF2 ,Cl2 F ,BrF2 ,IF2 and ICF2

GROUP - 18

Noble Gases - ns2np6, monoatomic, colourless, odourless, sparingly soluble in water because of weak
dispersion interaction. He has lowest boiling point, diffuses through glass, rubber or plastic
 Isolation : Except Rn all are present in atmosphere Ne, Ar, Kr and Xe are obtained as by products of
liquification of air and separated by fractional distillation.
 Xe–F compounds:
673K, 2ar
Xe(g)  F2 (g)   XeF2 (s)
(linear)
 873K, 7bar
Xe(g)  F2 (g)   XeF4 (s)
(square  planar)

573K,60  70bar
Xe(g)  3F2 (g)  XeF6 (s)
(distorted  octahedral)

Properties of xenon fluorides

Hydrolysis :
(a)  2Xe(g)  HF(aq)  O 2  g 
2XeF2 (g)  3H 2 O(l) 
(b) XeF2 + PF5  [XeF]+ + [PF6]– (fluoride donor)
(c) XeF4 + SbF5  [XeF3]+ [SbF6]
(d) XeF6 + MF  M+ [XeF7]– (fluoride acceptor)

Xe–O compounds
(a) 6XeF4 + 12H2O  4Xe + 4XeO3 + 24HF + 3O2
(b) XeF6 + H2O  XeO3 + 6HF (Partial hydrolysis)
(c) XeF6 + H2O  XeOF4 + 2HF
(d) XeO3  colourless explosive solid, trigonal pyramidal structure. Xe has sp3 hybridization.
(e) XeOF4  colourless volatile liquid.

XeO3  OH  HXeO 4  Xe  O 2  2H 2 O

(f) (disproportionation)