Extraction of aluminium

• Aluminium is usually extracted by the use of Hall

Heroult process. In this method, Al2O3 is melted
with cryolite [Na3AlF6] and electrolysed in
graphite lined steel tank which serve as cathode .
The anode are also made with graphite. the cell
runs continuously and at intervals molten
aluminum is drained from the bottom of cell and
more bauxite is added. When electric current is
passed, AlF3 from cryolite, ionises as
 Extraction of aluminium
• The overall reaction is: At the anode:
• AlF3 ↔ Al+++ + 3F- F- -e → F
F+F→ F2
• At the cathode: C (s) + O2- → CO (g) + 2e–
C (s) + 2O2- → CO2 (g) + 4e–
Al + 3e → Al
3+ –

• During the process of electrolysis, Aluminium

ions that are positively charged gain electrons
from the cathode and form molten aluminium
which is collected at the bottom of cell
Extraction of aluminium
 Uses of aluminium
1. Aluminium is used in a wide range of applications in the field of
transport, construction, etc.
2. Aluminium foils are used in the food industries for wrapping food.
3. It is used in the extraction of manganese and chromium from its
oxides.
4. As it is a soft metal and can be moulded into any shape it is used
in the manufacturing of storage cans.
5. It is mostly used with another metal in an alloy, meaning that it is
blended with another metal to create another compound with
some desirable characteristics-like stainless steel.
6. Aluminium being light, a good conductor of heat, corrosion-
resistant and cheap is used in making household appliances.
 Group IIIA
Group IIIA elements generally form covalent compounds.
Covalency is suggested by the followings:
1. Small size of the ions and their high charge of 3+ favours
the formation of covalent bonds. [Fajan’s rule]
2. The sum of the first three ionization energies is very large,
and this also suggests that bonds will be largely covalent.
3. Electronegativity values of these elements are higher
than for groups 1 and 2, and when reacting with other
elements the difference is not likely to be large.
 Halides of Aluminium
Preparation:
• By the action of Al (OH)3 on dilute HCl.
Al(OH)3 + 6HCl → AlCl3 + 3H2O
• By heating Al2O3 with coke and chlorine.
Al2O3 + C + 3Cl2 → 2 AlCl3 + 3CO2
• By heating Al2O3 with carbonyl chloride.
Al2O3 + 3COCl2 → 2AlCl3 + 3CO3
 Halides of Aluminium
Properties:
 White crystalline solid in its anhydrous form and hygroscopic in
nature.
 Aqueous solution of AlCl3 is acidic in nature
AlCl3 + 3H2O → Al (OH) 3 + 3HCl
 It gives whit ppt. with NH4OH.
AlCl3 + NH4OH → Al (OH) 3 ↓+ NH4Cl White PPt.
 It gives sodium meta aluminate with excess NaOH
AlCl3 + NaOH → NaAlO2 + 2H2O + 3NaCl
 It gives addition compound with ammonia.
AlCl3 + 6 NH3 → AlCl3.NH3
 Halides of Aluminium
Uses:
1. It acts as a catalyst in the manufacture of dyes, drugs
etc.
2. It is used in the manufacture of petrol.
3. It is used as catalyst in Friedel-Craft’s reaction.
Oxidation state
Group IIIA (13) all have three outer electrons.
They normally use these electrons to form three bonds,
giving an oxidation state of (+III).
 Structure of AlCl3 in anhydrous and aqueous form
Al+3 is small sized and highly charged. So, AlCl3 is covalent and exists
as dimer when anhydrous. But Al forms metal ion (Al3+) in solution.
This change from covalent to ionic happens because, the ions are
hydrated, and the amount of hydration energy evolved exceeds the
ionization energy.
In case of AlCl3, ionization energy required to convert Al to Al3+ is -
5137 KJMol-1 and total hydration energy evolved in solution is -5808
KJmol-1. Here hydration energy exceeds the ionization energy. So,
AlCl3 ionizes in solution.
The hydrated metal ions have six molecules of water which are held
very strongly in an octahedral structure
[Al(H2O)6]3+.
Structure of AlCl3 in anhydrous and aqueous form
 Inert pair effect
Some oxidation states shown by the elements of Gr IIIA, IVA and VA are:
IIIA (ns2 np1) → B & Al =+3 Ga, In & Tl = +3, +1
IVA (ns2 np2) → C & Si = +4 Ge, Sn & Pb = +4, +2
VA (ns2 np3) → N = +3, P, As, Sb & Bi = +3, +5
 From these oxidation state, it is found that higher elements show
two types of oxidation states.
 Higher oxidation states/group oxidation states are obtained when
all ns and np electrons involve in bonding.
 Lower oxidation states are obtained when only np electrons involve
in bonding. The lower oxidation states of these elements are found
more stable on descending a group.
 Causes of inert pair effect
Let us consider a group IIIA element. Outer electronic
configuration of elements is ns2 np1. Since np electrons
are farther away from the nucleus than ns electrons,
the np electrons are easily removed/excited to higher
orbitals than ns and hence two electrons of ns are
thought to be inert especially in the heaviest elements.
Two ns electrons remain paired and do not take part in
bonding because the energy required to unpair them is
more than energy evolved when they form bond.
 Inert pair effect
The greater stability of lower oxidation state
among heavier p-block elements is due to the
tendency of ns2 electron to remain paired and not
involved in bonding. This is called inert pair effect.
Eg: In Gr IIIA, Thallium (Tl) is quite unstable in the
+3 oxidation state and easily reduce to give more
stable +1 state. In Gr IVA, Pb+2 is more stable than
Pb+4.
 Inert pair effect with reference to group IIIA
B and Al show +3 oxidation state only, While Ga, In & Tl show +1 as
well as +3 oxidation states.
Group IIIA elements have outer electronic configuration ns2 np1.
When all 3 electrons are lost, we get +3 oxidation state. The stability
of +3 state decreases from Ga to Tl Ga+3 > In+3 > Tl+3 When only
one np electron is lost, +1 oxidation state is occured. In this case 2 ns
electrons in the inner shell remain paired and do not involve in
bonding. This is called inert pair effect. The stability of +1 oxidation
state increases Ga to Tl on descending the group. Ga+1 < In+1 < Tl+1
(Thallium) Tl is the lowest most element of group IIIA so, Tl+1 is
more stable than Tl+3
 Inert pair effect with reference to group IVA
 C and Si show +4 oxidation state While Ge, Sn & Pb show +2 as well
as +4 oxidation states.
 Group IVA elements have outer electronic configuration ns2 np2.
When all 4 electrons are lost, +4 oxidation state occurs. The stability
of +4 state decreases from Ge to Pb Ge+4 > Sn+4 > Pb+4
 When only two np electron are lost, +2 oxidation state occurs. In this
case 2 ns electrons in the inner shell remain paired and do not involve
in bonding. This is called inert pair effect. The stability of +2 oxidation
state increases Ge to Pb on descending the group. Ge+2 < Sn+2 <
Pb+2
 Pb is the lowest most element of group IVA so, Pb+2 is more stable
than Pb+4.
 Inert pair effect with reference to group IVA
 Compounds of Ge+2 and Sn+2 are less stable than Ge+4
and Sn+4. Therefore compound of Ge+2 and Sn+2 are
readily changed (oxidized) to Ge+4 and Sn+4. This means
compounds of Ge+2 and Sn+2 acts as reducing agent.

Ge 2
 
 Ge
oxidation 4
Sn 2 oxidation
  Sn 4
 Pb+2 compounds are more stable than Pb+4 and hence
Pb+4 are readily changed (reduced) into Pb+2. This means
Pb+4 acts as oxidizing agent.
4 2
Pb  
 Pb
reduction
 Inert pair effect with reference to group VA
The outer electronic configuration of group VA elements is ns2 np3
which suggest that these elements show +3 and +5 oxidation
states.
When all 5 electrons are lost, +5 oxidation state occurs. The stability
of +5 state decreases from N to Bi N+5 > P+5 > As+5 > Sb+5 > Bi+5
When only three np electron are lost, we get +3 oxidation state. In
this case 2 ns electrons in the inner shell remain paired and do not
involve in bonding. This is called inert pair effect. The stability of +3
oxidation state increases N to Bi on descending the group. N+3 <
P+3 < As+3 < Sb+3 < Bi+3 Bi is the lowest most element of group
IIIA so, Bi+3 is more stable than Bi+5.
 short notes on alumns
Aluminium ion may crystallize to form aqueous solution
forming double salt having general formula [M(H2O)6]
[Al(H2O)6](SO4)2, where M may be Na, K etc . The
crystals are usualy large octahedral extremely pure.
Alum is an inorganic compound composed of Water
molecules, Aluminum, other Metal than Aluminium,
and Sulphates. Alum is a double salt in the hydrated
form. Alum exists in different forms: Potash Alum, Soda
Alum, ammonium Alum.
 short notes on alums
Properties
Alums are highly soluble in Water.
These compounds are sweet in taste.
They generally crystallize in the regular octahedral form.
The Alum crystals get liquified when heated.
Alums generally exist in the form of a white and transparent
crystalline form.
When alum is dissolved in water double salts breaks up in solution
to their constituent ions crystals.s [M(H2O)6][Al(H2O)6](SO4)2
into [M(H2O)6]+, [Al(H2O)6]3+,
 short notes on alumns
Alum Water treatment is generally carried to treat the polluted
Water. These compounds act as a coagulant. It is a chemical Water
treatment technique typically applied prior to sedimentation and
filtration to enhance the ability of a treatment process to remove
particles
Uses
It is used as an acidulating agent in cooking.
It is used as a drying agent in a textile company.
It is used as an antiseptic agent.
We use it in the baking and picking process.
 Diborane and its structure
The electron deficient compounds are those in which the total
number of atomic orbitals available on the atoms of the compound
is more than the total number of valance shell electrons. In other
words, there are not enough valency electrons to form conventional
two electron cavalent bonds between all of the adjacent pairs of
atoms.
In diborane (B2H6) the total number of atomic orbitals are 14 (two
2s orbital on two B-atoms, six 2p orbitals on two B-atoms and six 1s
orbital on six H-atom) and that of valence shell electrons are only 12
(three from each B-atom and six from the H-atoms)
Diborane and its structure
 Diborane and its structure
Electron diffraction and IR study shows that B2H6 has hydrogen
bridged structure . Its 12 valence electrons are insufficient to form
the normal 2 electron 2 centred bonds, so that each boron atom
bonded to two terminal hydrogen atom H.) and other two with
common hydrogen bridge (Hb) and formed the banana bond called 2
electron - 3 centred (2e- 3C) bond.
The valence configuration of born atom at G.S. is 2s2 2p 1 and its
excited state becomes 2s1 2p1 2p1. The four atomic orbitals
hybridise together to give four sp3 orbitals in which one being
empty and remaining three being singly filled. Hence each boron
atom uses sp3 hybrid orbitals.
 Diborane and its structure
One singly, filled sp³ hybrid orbitals on B¹ atom, one empty sp 3
hybrid orbital on B2 atom and singly filled 1s atomic orbital on one
H{b} atom overlap together and form one bridging 2e- 3C bond, B¹
Нь- B² bond.
Similarly one empty sp3 hybrid orbital on B¹ atom, one singly filled
1s orbital on other H{b} atom overlap together and form other
bridging 2c - 3c bond.
Now remaining two singly filled s p3 hybrid orbitals overalp with
singly filled 1s orbital of H. atom to form normal 2e - 2c bonds,
 Some important questions answers
Q. BCl3 exists as monomer while AlCl3 exists as dimer. Give
reason.
Ans: Group IIIA elements (B, Al) have only three valency electrons.
When these are used to form three covalent bonds, the atom has a
share in only six electrons. The compounds are therefore electron
deficient. In BCl3 being B atom very small can get effective -overlap
and attain octet by - bonding with any one of the three Cl-atom. So it
does not need polymerize to remedy electron deficiency. But in
AlCl3, Al is larger and cannot get effective π overlap, so they
polymerize to remedy the electron deficiency. In this way AlCl3
exists as dimer.
 Some important questions answers
Q. BCl3 exists as monomer while AlCl3 exists as dimer. Give
reason.
 Some important questions answers
Q. Ρπ - Ρπ back bonding occurs in halide of Boron but not halide of Al. Why ?
BF3 is electron deficient compound. In BF3, being a B-atom very small can get
effective π-overalp and attain octet by -bonding with any one of the three
halogen atom. This bonding is called Ρπ-Ρπ backbonding. This back bonding is
formed between the empty 2P2 orbital on B-atom, which is not involved in
hybridisation and P-orbital of any one of the three halogen atom.

Halide of Al like AlCl3 is also electrondeficient. The size of Al is large, so it can

not get effective n-overlap with halogen and therefore Ρπ-Ρπ backbonding do
not occur in halide of Al. So, halides of Al are dimerised to Fulfill electron
deficiency.
 Some important questions answers
Q. Ρπ - Ρπ back bonding occurs in halide of Boron but not halide of
Al. Why ?