S and P Block Elements JEE/NEET/AIIMS/OLYMPIAD/KVPY

III A Group Boron Family

 Boron: Borax (Tincal) (Na2B4O7.10H2O), colemanite (Ca2B6O11 · 5H2O)
 Aluminium: Corundum (Al2O3), Diaspare (Al2O3.H2O), Bauxite (Al2O3,2H2O),
and cryolite (Na3AlF6).
 Ga is used in thermo couple to measure high temperature.
 From top to bottom lower oxidation state is prefered. Lower oxidation state is
having ionic behaviour.
 Al is most abedient metal on earth.
 Al reacts with N2 & O2 directly.
 Structure of Na2[B4O5(OH)4].8H2O

 B, Al, Ga, In and TI are the members of group 13. The general valence electronic
configuration of these elements is ns2 np1. The elements show +3 oxidation
state. Except boron other members also show +1 oxidation state.
 Boron always form covalent compounds. Other elements also form covalent
compounds when anhydrous like AlCl3, but in aqueous solution they give M3+
ions. Formation of M3+ ions is due to high hydration energy.
 Hardness : BN > Diamond > B4C3 > SiC
 BF3 < BCl3 < BBr3 < BI3 acidic strength
 BF3 is having back bonding and B.O. = 4/3

 H3BO3 is monobasic, Lewis acid, accept OH– and doesn’t give H+.

B(OH)3 + NaOH → Na + B− (OH)4

alcohol
H3BO3 + NaOH → Na 3BO3 [Burns with green flame]

6.9
 Tricks and Tech
 Borax. Na2B4O7.10H2O or Na2[B4O5(OH)4].8H2O
∆
       Na 2B4O7 → NaBO2 + B2O3  [Borax bead test] glassy mass

 3-Centre 2e– Bond in B2H6

∆
 B2H6 + NH3 
450K
→ B3N 3H6  (Borazole) (inorganic benzene)
 Inorganic benzene is more reactive than benzene.

 In B2H6 bridge bond is broken by a base.

1. +1 oxidation state of Tl and Ga is due to inert pair effect. The inert pair effect
is due to the fact that s-electrons are strongly held by nucleus, this results in
less availability of ns2 electron pair for bonding. The inert pair effect begins
after n ≥ 4 and increases with increase in value of n.
2. T1+ compounds resemble with compounds of alkali metals. Like alkali metals
hydroxides TlOH is water soluble and its aqueous solution is highly alkaline.
Tl2SO4 forms alum like alkali metal sulphates.
3. All halides of boron are electron deficient compounds (Lewis acids).
The order of Lewis acid strength
BF3 <BCI3 <BBr3 <BI3
BF3 is the weakest Lewis acid because it is less electron deficient due to back
donation of electrons from F atom. If central atom is different, the order of
acidic strength is
BCl3 > AlCl3 > GaCl3 > InCl3

6.10
S and P Block Elements JEE/NEET/AIIMS/OLYMPIAD/KVPY

4. BCI3 does not form a dimer but AlCl3 can form dimer because small sized boron
atom cannot hold the bridged CI atoms firmly due to large size of chlorine
atom.
5. The important minera1 of boron is borax (Na2B4O7. 10H2O) Borax when treated
with conc. HCl or H2SO4 gives crystals of basic acid. Borax gives coloured beads
with coloured salts. Coloured beads are formed due to the formation of metal
metaborates.
∆ 740°C
Na 2B4O7 .10H2O 
−10H O
→ Na 2B4O7 
→ 2NaBO2 + B2O3
2
glassy bead

CuSO4 + B2O3 → CuO.B2O4 + SO3

coloured bead

6. B3N3H6 is inorganic benzene or borazole. Both B and C are sp2 hybridised in

borazole. In diborane, B is sp3 hybridised while in BCl3 it is sp2 hybridised.
7. Bauxite is an important ore of aluminium. Red bauxite contains Fe2O3 as the
main impurity (removed by Baeyer's or Hall's process) while white bauxite
contains SiO2 as the main impurity (removed by Serpeck's process). Aluminium
is obtained by the electrolysis of alumina dissolved in fused cryolite and it is
refined by Hoope's electrolytic process.
 Aluminum is a strong reducing agent and can reduce oxides which are not
reduced even by carbon. This is due to lower ionisation energy of aluminium
than carbon. The reducing character of these elements is Al > Ga > In> Tl.
 Boron forms a large no of volatile covalent hybrides, known as boranes e.g.
B2H6, B4H10, B6H10, B5H11. Two series of boranes with general formula
BnHn+4 and BnHn+6 are more important.
 The acidic nature of oxides and hydroxides changes from acidic to basic
through amphoteric from B to Tl.
B2O3 and B(OH)3 > Al 2O3 and Al(OH)3 >
(acidic ) Amphoteric
Ga 2O3 and Ga(OH)3 > ln2 O3 ln(OH)3 > Tl 3O3Tl(OH)3
( Amphoteric) (basic ) (strong basic)

 Concentrated nitric acid oxidises boron to boric acid but no such action is
noticed other group members.
B + 3HNO3 → H3BO3 + 3NO2

6.11
 Tricks and Tech
Ores of Boron
Borax or tincal: Na2B4O7.10H2O
Kernite or Rasorite: Na2B4O7.4H2O
Colemanite: Ca2B6O11.5H2O
Orthoboric acid: H3BO3

Purification
(i) Baeyers's Process:
Roasted +(Caustic soda solution)
Bauxite 
FeO → Fe O
→ Roasted or 
High pressure (150°C, 80 atm)
→
Finely powdered 2 3
(red) Filtered, Fe2O3 as residuce

(ii) Hall's Process:

+ Na CO CO
Bauxite  2 3
Fused, extracted with
→ Solution  2
50 − 60°C, and Filtered
→
Finely powdered
water Reesiduce Fe2O3 Filtered,(Na 2CO3 )
(red)

(iii) Serpeck's Process:

+ Coke + N
Bauxite  2
Heated to1800°C

→
Finely powdered
( white)

Sillica reduced to Si which volatalises + Alumina form aluminium nitride

Hydrolysis Heated
AlN → Al(OH)3 → Pure Al 2O3

Some important alums are: M2SO4.M2(SO4)3.24H2O

Potash alum K2SO4.Al2(SO4)3.24H2O

Sodium alum Na2SO4.Al2(SO4)3.24H2O
Ammonium alum (NH4)2SO4.Al2(SO4)3.24H2O
Chrom alum K2SO4.Cr2(SO4)3.24H2O
Li+ does not form alum.

6.12
S and P Block Elements JEE/NEET/AIIMS/OLYMPIAD/KVPY

Group IV Carbon Family

1. SiF4 behaves as Lewis acid and can accept lone pair of electron of ligand due
to presence of vacant d-orbitals in silicon.
– –
SiF4 +2F → SiF6
2. Tin upon reaction with NaOH form sodium starinite and with conc. HNO3
forms meta stannic acid, For example
Sn + 2NaOH + 4H2O → Na2SnO3 + 2H2
Sn + 4HNO3 → H2SnO34NO2 +H2O
p-block of the periodic table is unique as it contains all types of elements:
metals, nonmetals and metalloid. There are six groups of p-block elements in
the periodic table numbering from 13 to 18. The first member of p-block differ
from the remaining members of their corresponding group in two major respects
i.e., first is the size and other is the availability of d-orbitals. The combined
effect of size and availability of d-orbitals influence the ability of these elements
to form p bonds. Lighter elements form pp–pp bonding while heavier ones form
dp–pp or dp–dp bonds.
3. Carbon is a typical non metal forming covalent bonds employing all its four
valence electrons (2s2 2p2). It shows the property of catenation, the ability to
form chains or rings not only with C—C single bonds but also with multiple
bonds (C = C or C ≡ C).
The tendency to catenation decreases as C >> Si > Ge = Sn > Pb.
4. Three important allotropes of carbon are diamond, graphite and fullerenes.
The members of the carbon family mainly exhibit +4 and +2 oxidation states.
Compound in +4 oxidation states are generally covalent in nature. The tendency
to show +2 oxidation state increases among heavier elements due to inert pair
effect.
5. Carbon forms two important oxides i.e., CO and CO2, CO is neutral while
CO2 is acidic. CO forms metal carbons because it has lone pair of electrons on
carbon, It is deadly poisonous due to higher stability of its hemoglobin complex
as compare to that of oxy hemoglobin complex. Increased content of CO2 in
air causes increase in green house effect.
6. The mixture of CO and H2 is known as water gas or synthesis gas and a
mixture of CO and N2 is known as producer gas. These are very important
industrial fuels. CO is a colourless, odourless and almost water insoluble gas.
It is a powerful reducing agent and reduces almost all metal oxides other than
alkali and alkaline earth metals,
7. Solid form of CO2 is known as dry ice. Dry ice is used as a refrigerant for
ice-cream and frozen food. Gaseous CO2 is used to carbonate soft drinks and
as a fire extinguisher.
6.13
 Tricks and Tech
8. 'SiO2 is a covalent, three dimensional network solid in which each silicon
atom is covalently bonded in a tetrahedral manner to four oxygen atoms and
each oxygen atom in turn covalently bonded to another Si atoms. Quartz is a
crystalline form of silica and it is extensively used as a piezoelectric material.
9. Silicones are a group of organosilicon polymers which have (R2SiO) as a
repeating unit. The starting materials for the manufacture of silicones are alkyl
or aryl substituted silicon chlorides, RnSiCl(4–n) where R is acyl or aryl group.
The chain length of polymer can be controlled by adding (CH3)3SiCl which
blocks the ends. Silicones are hydrophobic in nature, used as sealant, greases,
electrical insulators and for water proofing fabrics.
10. Zeolites, mica and asbestos are some examples of silicates. The basic structural
4–
unit of silicate is SiO4 . In silicates either the discrete unit is present or a
number of such units are joined together via corners by sharing l, 2, 3 or 4
oxygen atoms per silicate units. Glass and cement are two important man made
silicates.
11. Zeolites are aluminosilicates obtained when few Si atoms in three dimensional
network of SiO2 are replaced by aluminium atoms. These are widely used as a
catalyst in petrochemical industry for cracking of hydrocarbons and isomerisation
eg. ZSM–5. Hydrated zeolites are used as ion exchangers in softening of hard
water.

Some Important Points

Stability order is as because lower O.N. is pretered by lower one.
Ge+2 < Sn+2 < Pb+2
Ge+4 > Sn+4 > Pb+4
PbCl4 is good oxidiser because it converts into PbCl2.
 Diamond is harder than graphite but thermally less stable than graphite.
 Graphite is good conductor due to p-electron.
 Graphite is Sp2 hybridised while diamond is Sp3.
 Purest form of carbon is fullerenes.
 SnCl4.5H2O is called 'butter of tin' and it is used as a mordant in dyeing.
   C Si Ge Sn Pb
Non-metals    metalloid         metal         metal
 Ge, Sn and Pb also exhibit +2 oxidation state due to inert pair effect.
 Sn2+ and Pb2+ show ionic nature.
 The tendency to form +2 ionic state incerases on moving down the group due
to inert pair effect.
FeO Green
Fe2O3  Brown
MnO2      Light pink; in excess black.

6.14
S and P Block Elements JEE/NEET/AIIMS/OLYMPIAD/KVPY

 The phenomenon of adding broken glass pieces during glass making is called
cullet.
Soft glass: Mixture of Na and Ca silicates
Hard glass: Mixture of K and Ca silicates.
Pyrex glass and Jena glass: Mixture of Zn and Ba borosilicates resistant to
heat, shock and common reagents.
 Glass is attacked by HF. This property is used in the etching of glass.
1. Silicones: Silicones are polymeric organosilicon compound containing Si—O—Si
linkage. They have high thermal stability of Si—O—Si chaines and are also called
high temperature polymers.­
Their general fomula is (R2SiO)n. Where R= –CH3, —C2H5—C6H5.
4–
 Ortho silicates contain discrete SiO4 tetrahedra e.g., Phenacite (Be2SiO4);
Willemite (Zn2SiO4); Olivine (9Mg2SiO4.Fe2SiO4); Zircon (ZrSiO4) .
4–
 Pyrosilicates are the simplest condensed silicates in which two SiO4
6–
tetrahedra are joined by one oxygen atom forming discrete SiO7 ion e.g.,
Thoreveitte Sc2(Si2O7)3 and hemimorphite, Zn3(Si2O7).Zn(OH)2.H2O
Example : (a) Synthetic silicates are Li2SiO3 and Na2SiO3.
    (b) Pyroxene mixtures like spodumene. LiAl(SiO3)2 Jadeite, NaAl(SiO3)2,
Enstatile, MgSiO3 and diopside CaMg(SiO3)2.
2. Chain Silicates are of two types:
2– 6–) units
 Having (SiO3 )n units Having (Si4O11 n
 Ordinary glass is manufactured by fusing together a mixture of sand,
Na2CO3 and lime stone (usually in the ratio 330 : 100 : 50). Owing to
its complexity a super cooled liquid of silicates.
 The hardness order of some abrasive is
Diamond > Boron carbide (B4C) > Silicon carbide (SiC)
 Cyanogens (CN)2 is pseudohalogen
 Diamond does not react with halogen while graphite reacts.
 Graphite on heating with cone. HNO3 given benzene hexa carboxylic acid
(C12H6O12) i.e., 

6.15
 Tricks and Tech
 PbCl2 is more ionic than PbCl4 (Covalent)
 (CH3COO)2 Pb is called sugar of lead.
 SnCl4.5H2O is called butter of tin. Pb3O4 is called red lead or Sindur.
 Oxides: carbon forms five oxides CO, CO2, C3O2
CO, C ≡ O, CO2, O = C = O, C3O2 O = C = C = C = O

 SiO is not possible while SiO2 is Sp3 hybridised

 The red form of PbO is called litharge and the yellow form is massicot.
Pb3O4 (red lead or Sindur)
3. Halides: Elements of group 14 react with halogens directly to form tetrahedral
and covalent halides except C where its halide is produced by the action of
halogens on hydrocarbons. PbBr4 and Pbl4 do not exist because Pb4+ is a strong
oxidant and Br– and I– are strong reductants. Hence Pb4+ ion is difficult to
survive in pressure of strong reductants Br– and I– and is immediately reduced
to Pb2+ ion.
4. Salt like carbides: These carbides are formed by the metals of group IA, IIA,
IIIA (except boron), coinage metals, Zinc, cadmium & some lanthanides.
Acetylides: These are ionic carbides which yield acetylene on hydrolysis. The
alkali metals and copper, silver and gold form M2C2 type compounds. these
contain C22– ions methanides. These carbides evolve methane on hydrolysis.
Al4C3, Be2C, Mn3C etc. are some of methanides. These contains C4– groups.
5. Allylides: These carbides evolve allylene (methyl acetylene) on hydrolysis. This
type of the carbides is only Mg2C3. It contains C34– discrete group.
Thus elements like Si, Ge, Sn and Pb have an ability to increase their co-
ordination number form four to six. Other examples of hexa co-ordinated species
are:
[GeF6]2–, [SnCl6]2–, [PbCl6]2– etc.

6.16