Group 1 element

Electronic configuration
Atomic radii
Ionization Enthalpy
Metallic Character
Melting and boiling point
Density
Chemical properties
Anomalous Behaviour of
Boron

Allotropes
Diamond
Graphite
P - Block Elements Fullerence

Group 1 element

Electronic configuration
Atomic radii
Ionization Enthalpy
Electronegativity
Physical properties
Chemical properties
Anomalous Behaviour of Carbon
 The P-Block
Elements
P- Block elements 6 groups

13 14 15 16 17 18

III A IV A VA VI A VII A VIII A

Group -13 Elements Boron family

Non - Metal

{B } { Al Ga In Ti }
Metal

Occurence - Boron occurs in two is isotropic forms ¹⁰B

19% and ¹¹B 81% . Its abundan in Earth's crust is very
low 0.0001% by mass
Boron mainly occurs as orthoboric acid H3BO3 .
Boron Na2B407•10H20 or {Na, [B4O5 OH 4]8H20}
general formula correct formula

Kernite NO2[B4O5 OH 4]
Colemanite Ca2[B304 OH 3]2.
Aluminium is the third most abundant element by weight
8.3% found in the Earth's crust after oxygen 45.5% and
silicon 27.7%

The important mineral of Al are:-

i Bauxite Al2 O3•2H2 O
ii Cryolite Na3 Al F6
iii Mica K2O •3Al2O3 •6SiO2 • 2H2O
iv Corundum Al2O3
v Beryl 3BlO•Al2O3 •6SiO2

• Gallium, Indium and Thallium TL are less abundant than

aluminium. Highest concentration of Ga 0.1-1% is found in the
mineral germanite traces of indium are found in the sulphide
ares of sulphide ore of Zn while that of thallium Tl are found
in the sulphide ores of Pb.

Electronic Configuration
Outershell electronic configuration of group 13 elements
ns²np¹ where n=2 to 6 or 7

Example:- B 5 :- 1s²,2s²2p¹
Al 13 :- 1s² , 2s²2p⁶,3s²,3s¹
Ga 31 :- 1s²,2s²2p⁶,3s²3p⁶3d¹⁰,4s² 4p¹
In 49 :- [Kr] 4d¹⁰5s²5p¹
Tl 81 :-[Xe] 4f¹⁴ 5d¹⁰ 6s² 6p¹
Atomic radii
On moving down the group,atomic radii and ionic radii
with some irregularities due to increase in no. of shells.

[B < Ga < Al < In <Tl]

Atomic radii of Ga is smaller than that of Al due to poor

shielding effect of 3d - electron in gallium.

Ionization Enthalpy
Ionisation enthalpies decreases down the group
with some irregularities

[B > Al < Ga > In < Tl] orders of ΔiH1

[B > Tl > Ga >Al > In]

• First ionisation enthalpy of galium is

more than that of Al due to poor shielding effect of 3-d
elections in gallium.
•First ionisation enthalpy of Tl is more than that of Al due to
poor shielding of 4f electrons in Thallium:

Electronegativity
Electronegativity decreases down the group with
some irregularities.
[B >Tl > In> Ga > Al]
Metallic character
An moving down the greeps metallic character increases
from Be to Al from then decrease from Al to Tl.

[B < Al > Ga > In> Tl]

Al is most metallic due to its low ionization enthalpy.

Melting points and Boiling points

Melting point decrease on moving down the group from

B to Ga and then increase from Ga to Tl.

[B >Al > Ga < In <Tl]

Melting point of boron is highest due to its crystalline

structure.

Boiling point of these elements decrease regularly in

moving down the group.
[B > Al > Ga > In >Tl]

Density

On moving down the group, densities Increases due to

increase in atomic mass more than that of atomic volume.
Chemical properties of group 13 elements
As we move down the group, the tendancy of selections of
the valence shell to participate in bond formation decrease.
This reluctance of the s-electron to participate in bond
formation is called inext pairs effect. This is due to poor
shielding of ns, electron of the valence shell by intervening d-
sf- electron.

Inext pair effects is observed in p-block elements.

•Oxidation state

Ground state configuration

Excited state configuration

The most common oxidation states of group B

elements are +3 and +1.

The stability of +3 oxidation state decreases moving

down the group due to inert pair effect.

The stability of +1 oxidation state increase on moving

down the group due to inert pair effect.
 B +3
Al +3
Ga +3 +1
In +3 +1
Tl +1

• The sum of first three ionisation enthalpie of

boron is very high. Therefore, Boron does not
form B3+ Ion and compounds of boron are
covalent in nature.

•Aluminium forms covalent compounds except AlF3

ionic .

•Compounds of Boron are electron deficient due to

presence of 6e- on boron atom. Therefore, compounds
of boron acts as lewis acid.

Example :- BCl3 Lewis Acid accepts a lone pair of

electrons from ammonia to form adduct BCl3, NH3 .
addition product
• Halides of boron are easily hydrolysed by water due to
electron deficiency on boron atom.

BCL3 + 3H2O ----- B OH 3 + 3HCL

B OH 3 + H+OH- -------- [B OH 4]- + H+

•Boron trihalides form [B OH 4]- tetrahedral unit from water.

•AlCl3 on hydralysis gives octahedral [Al H2O6]3+ species
sp³d² because Al due to the presence of 3d-orbitals can
expand its covalency from 4 to 6.

•AlCl3 form dimer Al2Cl6 due to electron deficiency

on Aluminium atom.

•Boron halides BCl3, BBr3,BI3 do not form dimer. This is

due to the reason that boron atom is too small that it
cannot accomodate for large sized halogen atom around
it.
•Boron triflouride BF3 does not form dimer due to back
bonding.
•Crystalline structure of boron consist of isolated unit in
which Boron atom on 12 corner and it has 20 faces
•Reactivity towards air
•Boron is unreactive in crystal form.
•Aluminium forms a very thin oxide on the surface which
protects Al from further attack.
•Amorphous boron and aluminium metal on heating in air
form B2O3 & Al2O3.

2E + 3O2 ------ 2E2O3

•B & Al on reating with N₂ at high temp. form nitrides.

2E + N2 ------ 2EN
Where E B,Al,Ga,In

K³B:- a In case Tl,Tl2O ,Tl3N forms.

b B3O3 is acidic
Al3O3 and Ga2O3 --- amphoteric oxides
In2O3 and Tl2O ---- Basic oxides

•Reactivity towards acids and Alkalies

•Boron does not react with acids & alkalies.

•Al is an amphoteric element. Therefore Al reacts with acids
and bases.
2Al s + 6HCl aq 2AlCl3 aq + 3H2 g
2Al s + 2NaOH aq + 6H₂O 1 ----------- 2 Na [Al OH 4]-
+ 3H2 g

•Al reacts with nitric acid HNO3 to form protective layer of

aluminium oxide on its surface. Therefore, nitric acid HNO3
can be transported in aluminium container
Reactivity towards Halogens

Group 13 elements reacts with halogens to form trihalides

EX3 .Except Tl forms monohalides TLX because the most
stable oxidation state of Tl is +1 due to inert pair effect.
where E B, Al, Ga, In & X F, Cl, Br, I .

•Thallium forms only one Trihalides TlI3 in which Tl+ I3-

ions exist.
• Acidic strength of boron trihalides
BF3< BCL3< BBr3 <B I₂

•Trihalides of group 13 elements acts as lewis

acid due to electron deficiency in central atom.

•Trihalides of group 13 elements form dimer to achieve

stable configuration or to complete octet.
•In structure of BF4- boron atom is sp³ hybrid and
BF4- is tetrahedral species.B- F bond is purely single
bonds

ANOMALOUS BEHAVIOUR OF BORON

Anomalous properties of boron is due to
i its small size
ii high electron negativity
iii Absence of d-orbitals in its valence thell

Some important anomalous properties of boron are:-

•Boron is harder than other elements.
•Oxide and hydroxide of boron are acidic nature.
•Max- covalency of boron is 4 whereas max covalency
of other elements is more than 4.
•Boron forms [BF4]- ions whereas Al forms [AlF6]-
ions.

Uses of Boron:-
•Boron fibres are used in making bulletproof vests and light
composite material for aircrafts.
•Aqueous solution of orthoboric acid H3BO3 is used as
antiseptic for eyes .
Uses of Aluminium
•Aluminium is a good conductor of electricity Therefore, it is
used for making transmiss cables.

• Al foil is used for wrapping fine articles like photographic

films, medicines, cigarette sweets, etc.

GROUP 14 ELEMENTS

C, Si , Ge , Sn ,Pb

Occurrences- Carbon is the seventeenth most abundant

element by weight in the earth's crust. It occurs in the native
state in form of coal, graphite and diamond. It combine state, it
occur widely as metal carbonates, hydrocarbon
carbohydrates, CO2. It contains isotopes ¹²C, ¹³C,¹⁴C.¹⁴C is a
radioactive isotope with a half life of 5570 years and it is used
for radio carbon dating.

Silicon is the second 27.7% most abundant element by

weight in the Earth's crust. It occurs in form of silica SiO2 and
in a wide variety of silicates and clays. Germanium occurs in
traces.

Ultrapure form of Ge and Si are used to make transistors and

semiconductors devices. Sn occurs as tine stone or cassiterite
SnO2 . Pb accurs as galena PbS which is associated with
ZnS zinc blende . The ores of Pb are anglesite PbS04 and
cerussite PbCO3 .
Electronic configuration:-
ns'np² where n 2 to 6

Atomic radii
increases down the group.

Ionization enthalpy
First IE of group 14 elements are higher than those of
group 13 elements

Electronegativity
Increases from C to si then constant

Physical Properties
•Metallic character - On moving group, metallic character
increases.
C Si Ge Sn Pb

It is due to decrease in ionization energy.

•Melting and boiling points -

M.P. and B.P. of group 14 elements are much higher than
those of corresponding group 13 elements. This is due
to the reason that atoms of group 14 form covalent
bonds with each other and hence strong bonds exists
among them.
On moving down the group, M.P. and B.P. decrease due
to decrease in magnitude of interatomic force with
increase in atomic sizes.

Exception:- M.P. of tin Sn is less than that of lead.

Chemical Properties

Oxidation state
ns² np²

Ground state

Excited state

Most common oxidation state of group elements are +4 and

+2.
C,Si, Ge ,Sn +4 +2 stable
Pb +4 <+2 stable
This is due to inert pair effect.
•On moving down the group, stability of +4 0.5 decrease due
to inert pair effect.
•On moving down the group,stability of +2 0.5Nincrease due
to inert pair effect.
•Compounds in +4 oxidation state are covalent.Because the
sum of first four ionisation enthalpies of these elements are
very high.
•Compounds of +2 oxidation state are more ionic than that
of compounds in +4 oxidation state.
•Ionic character increase on moving down the group due to
decrease in ionization enthalpies.
•PbO3or P IV acts as strong oxidising agent. This is because
in Oxidation state of PB is + 4 which is unstable due to the
inert pair effect.Therefore PbO2 is converted into PbO by
release of Oxygen and PbO2 act as oxidizing agent
 Reactivity towards oxygen
Group 14 elements on heating with oxygen form
two types of oxides [EO & EO2]
CO CO2
SiO SiO2
GeO GeO2
SnO SnO2
PbO PbO2

SiO exists at only high temperature.

Acidic strength with in E.N.
Acidic strength with in oxidation state.

Reactivity towards Water

•Carbon ,Silicon and germanium are not affected by water.

•Tin reacts with steam to form SnO2 & H2 gases.

Sn +2H2O g --------- SnO2 +H2

•Lead does not react with water due to presence of

protective oxide layer in it.

Reactivity towards halogens

•Group 19 elements form two types of halide of
formula MX2 and MX4.
where M Si, Ge , Si, Pb X F,CL,Br,I

•Except carbon, all others members react directly

with halogen under suitable conditions to make
halides.
•Tetrahalides MX are cevalent in nature.
• In tetrahalides, central atom is sp² hybridized and
forms molecule is tetrahedral.
•Exception:- SnF4 and PbF4 are ionic in nature
•PbI4 does not exist because PbI bond initially formed during
the reaction does not release enough energy to unpaired 6s²
electrons and excite one of them to highest orbital to have
four unpaired electrons around lead atoms
•Stability of tetrahalides MX4 decrease down the group and
stability of dihalides MX4 increase down the group due to
inert pair effect.
Example :-PbCl2 id more stable and SnCl2 and SnCl4 is more
stable than PbCl4. •Tetrahalides are except CX4 are easily
hydrolysed.
SnCl4 4H2O ----- Si OH 4 4HCl

•CX4 like CCL4 is not hydrolysed due to absence of empty

orbital in valence shell of carbon atom.

•PbX4 is more stable than PbX2.This is because +4 oxidation

state of Pb is more stable than +2 oxidation state due to inert
pair effect.

Q1 [SF6]²- is known whereas [SiCl6]²- not.

Give possible reason ?
Solution The main reasons are -
i Six large sized chloride ions cannot be
accomodated around small size Si⁴ ions
ii Interaction between lone pair of chloride ion.
and Si4 is not very strong.
Q2 White fumes appears around the bottle of anhydrous
aluminium chloride. Give reason?
Solution Anhydrous AlCl3, is partially hydrolysed with
moisture to liberate HCl gas. Most HCl gas Appears white in
colour.

Anomalous behaviour of carbon

Anomalous properties of carbon are due to
i its small size.
ii High electronegativity
iii High ionisation enthalpy
iv Absence of d-orbital in its valence shell

Some important anomalous properties of carbon are-

1 Carbon in form of diamond is very hard as
compared to the other elements of group 14.
2 Carbon has only four valence orbitals one 2s and
three 2p . Therefore, its max. covalency is four
whereas other elements of group due to presence of
d-orbital this can expend their covalency to Six. Thus,
carbon does not form CF6²-Ion whereas silicon forms
SiF6²- ion.
3 Carbon has higher melting and boiling points than
other members of the group.

4 Due to small size and high electronegativity carbon

has a strong tendancy to form pπ-pπ multiple bonds
either with itself or with other atoms such as oxygen
c 0 ,nitrogen C triple N and sulphur c 5 unstable
, the remaining elements do not form pπ pπ bonds
because & their bigger size.Instead due to the
presence of d-orbitals they form dπ-pπ multiple
bonds.
5 Catenation:- Carbon has highest catenation due to high bond
dissociation energy of C-C bond. On moving down the group,
catenation decrease.
C Si Ge Sn Pb.

Allotropes
The phenomenon of existence of an element in two or
more forms which have different physical properties but
identical chemical properties is called allotropy and the
different forms are called allotropes.

Allotropes of Carbon
Crystalline Diamond
Graphite
Fullerene

Amorphous Coke
Charcoal
Carbon Black

Diamond
•Structure Carbon is sp² hybridized
3-D network solid

•Hardness It is hardest substance due to their 3-D network

structure.
•Conductivity Bad conductor of electricity
•Uses Because of its hardness, it is used
for cutting glass,for making borers for rock,driling and for
making abrasives.
Graphite
•Structure Carbon is sp²-hybridized
It has 2-D sheet like structure layered in which benzene
ring fused together .Force between layers is vander
waal's
•Softness Due to presence of weak vande waal's
force between layers one layer can slip over the other.
This makes graphite soft and a good lubricating agent.
•Conductivity It is good conductor of electricity due
to presence of free electrons. Therefore, it is used in
making of electrodes of batteries.
Thermodynamically, graphite is more stable than
diamond.

Fullerenes buck minster fullerene

Preparation- Graphite --------- vapours Cn upto 350

C60 & C70 ---- Main component & trance

C 60 C 70
•sp² hybridized •sp² hybridized
• 12 five membered ring • 12 five membered ring
•20 six membered ring •25 six membered ring

•Five membered ring his surrounding by only six membered

ring.
•Fullerene is the purest form of carbon because it does not
form dangling bond.