INORGANIC CHEMISTRY

CHM 003
Position of p-block in periodic table
 Introduction
They are group IIIA or 13 elements
Boron, Aluminium, Gallium, Indium and
Thallium
First post-transition elements
 Introduction
 Impure (amorphous) boron is a brown powder, but the
pure element forms shiny, silver-grey crystals.

 It has high melting point and low electrical

conductivity, hence serves as refractory material
 Introduction
Aluminium is a hard, white metal.

 Thermodynamically, it should react with air and

water but it is resistant because of the formation
of an oxide layer.

The thickness of the oxide can be up to 10-6 to 10-4

mm.
 Introduction
A thicker layer of Al2O3 can be obtained by
making Al the anode in the electrolysis of H2SO4.
The result is anodized aluminium which will take
up dyes and pigments used in decorative finish.
 Introduction
Gallium is a silver-coloured metal with a
particularly long liquid range (303–2477 K).
Indium and thallium are soft metals, and indium
has the unusual property of emitting a high-
pitched ‘cry’
 Introduction
Property
B Al Ga In Tl

Atomic number
5 13 31 49 81

Outer electrons
2s22p1 3s23p1 4s24p1 5s25p1 6s26p1

Physical state
Solid Solid Solid Solid Solid
 Introduction
Property B Al Ga In Tl

Melting point (oC) 2300 660 29.8 156.6 303.5

Boiling point (oC) 2550 2367 2403 2080 1457

Density (g/cm3) 2.3 2.70 5.91 7.31 11.85

 Introduction
Property B Al Ga In Tl

Atomic radius (A) 0.85 1.43 1.38 1.67 1.70

Ionic radius, M3+ (0.20)* 0.68 0.76 0.94 1.03

Electronegativity 2.0 1.5 1.7 1.6 1.6

 Introduction
Property B Al Ga In Tl

E0 (volts): (-0.90)* -2.37 -2.87 -2.89 -2.90

Oxidation states -3 to +3 +3 +1, +3 +1, +3 +1, +3

∆H0hydratn (kJ/mol) - -4750 -4703 -4159 -4117

 Introduction
Property B Al Ga In Tl
M(g) → M(g) + e-
M (g) → M (g) +
+ 2+ 801 578 579 558 589
e-
M2+(g) → M3+(g) + 2427 1817 1971 1813 1961
e-
3660 2745 2952 2692 2867
 Aluminum and other group 13 elements
 The sum of the first three ionization energies of Boron is
higher than those of the other members of the group.
enthalpies is less, as compared to Boron.
 Thus, it is difficult to lose electrons.
 In the last three elements, both +1 and +3 oxidation states
are seen.
 The +1 is because the nucleus holds the outer most s
electrons tightly. Thus, only p bonding may be available for
bonding.
 The compounds in +1 state are more ionic than those in +3
state.
 Introduction
Of the five Group III or 13 elements, only boron
and aluminium are reasonably familiar elements.
Aluminium is in fact the most abundant metal,
the third most abundant element in nature.
The other elements are rare and boron is the only
one so far found in concentrated deposits.
 Introduction
 Group 13 or III show a wide variation in
properties:
Boron (B) is a non-metal
Aluminium is a metal but exhibits many chemical
properties similar to boron
 Gallium, Indium and Thallium are metals
 Introduction
 Diagonal relationship exist between
aluminium and beryllium
The M(III) oxidation state is
characteristic for elements in group 13.
The M(I) state occurs for all group 13
elements except B
 Introduction
For thallium (Tl) the +1 state is the more
stable oxidation state.
Thallium shows similarities to elements
outside those in group 13
Show similarities to the alkali metals, Ag, Hg
and Pb.
 Introduction
Chemically, boron has tendency to form
covalent bonds.
It shares more similarities with carbon and
silicon than with aluminium and the other
Group 13 elements.
In contrast to the later elements, boron
forms a large number of compounds.
 Introduction
Likecarbon, boron forms many hydrides.
Like silicon, it forms oxygen-containing
minerals with complex structures (borates).
The compounds are called clusters.
They are “electron-deficient” cluster
compounds.
 Occurrence

The most common minerals containing boron

are the tetraborates of sodium or calcium.
The main sources of boron are borax,
Na2B4O7.10H2O and
kernite, Na2B4O7.4H2O
 Occurrence
Aluminium is not found free in nature.
Its compounds are widespread.
 It is the most abundant metal in the earth's
crust.
After oxygen and silicon, aluminium is the
most common element in the Earth’s crust
(8.1%)
 Occurrence
Aluminosilicates such as clay, kaolin (or china
clay), mica and feldspar are well known and
widely distributed.
The oxide, Al2O3 occurs (anhydrous) as corundum
and emery.
 (hydrated) as bauxite Al2O3.2H2O.
 Cryolite. Na3AlF6. (sodium hexafluoroaluminate).
 Occurrence
Gallium, indium and thallium occur in trace
amounts as sulphides in various minerals.
 It occur as minor components of a range of
minerals, such as sphalerite (ZnS).
 EXTRACTION

Each can be extracted by reduction of their

respective oxide at high temperature.
Using either carbon or hydrogen
Or by electrolysis of an aqueous solution of a salt
of the required element.
Of the group 13 elements, aluminium is of the
greatest commercial importance with uses
exceeding those of all metals except iron.
 Extraction
Its isolation from the widely available
aluminosilicate minerals is prohibitively difficult.
Bauxite and cryolite are the chief ores, and both
are consumed in the extraction process.
Aluminium is obtained on a large scale by the
electrolysis of the oxide, dissolved in fused
cryolite
 Extraction
The oxide, occurring naturally as bauxite,
Al2O3.2H2O, usually contains silica, titanium
dioxide and iron(III) oxide as impurities.
Bauxite contains only 30-54 % aluminium oxide
(alumina).
The impurities must be removed first, usually by
the Bayer process.
This is because aluminium, once prepared,
cannot be freed of the impurities.
 Extraction
The crude oxide is dissolved under pressure in
caustic soda solution
The aluminium oxide and silica dissolved and the
iron(III) oxide is left:
Al2O3 + 2OH- + 7H2O 2[Al(OH)4(H2O)2]-
From the sodium aluminate solution, aluminium
hydroxide is precipitated by passing in carbon
dioxide: 2[Al(OH)4(H2O)2]- + H2O + CO 2 →
2[Al(OH)3(H2O)3] + CO32-
 Extraction
Alternatively, the solution is 'seeded' with a little
previously prepared aluminium hydroxide:
2[Al(OH)4(H2O)2]- + H2O → 2[Al(OH)3(H2O)3] + OH-
The pure oxide is then obtained by heating
the precipitated hydroxide:
 2Al(OH)2(H2O)3 → Al2O3 + 6H2O
The pure oxide is dissolved in molten cryolite in an
iron bath lined with graphite which acts as the
cathode
 Extraction
Aluminum is extracted from the Al2O3 by
the Hall-Heroult, an electrolytic process.
The anode consists of carbon rods
suspended in the molten electrolyte.
A low voltage must be used to avoid
decomposition of the cryolite.
 Extraction
Aluminium is more dense than the
alumina/cryolite solution
It falls to the bottom of the cell where it can be
collected as pure liquid metal.
Molten aluminium is run off at intervals, fresh
alumina being added as required.
Oxygen is evolved at the anode
It is slowly attacked to form oxides of carbon.
 Extraction
A little carbon tetrafluoride, CF4, may
also be formed by slight electrolysis of
the cryolite.
Silicon nitride has been used to replace
graphite for the bath lining
It is very resistant to molten aluminium
and cryolite.
 EXTRACTION OF ALUMINIUM

OXIDATION (LOSS OF ELECTRONS)

TAKES PLACE AT THE ANODE
ELECTRONS
CARBON ANODE
POSITIVE
ALUMINIUM
IONS ARE STEEL CARBON ANODE
ATTRACTED CATHODE
TO THE
NEGATIVE CARBON
CATHODE
LINING
MOLTEN
ALUMINA and
CRYOLITE CARBON CATHODE

Al3+ + 3e- Al REDUCTION (GAIN OF

ELECTRONS) TAKES
O2- O + 2e- PLACE AT THE CATHODE

ANODE 3O2- 1½O2 + 6e- OXIDATION

CATHODE 2Al3+ + 6e- 2Al REDUCTION

 EXTRACTION OF ALUMINIUM

CARBON DIOXIDE

PROBLEM
CARBON ANODE
THE CARBON
ANODES REACT WITH
THE OXYGEN TO
PRODUCE CARBON
DIOXIDE

THE ANODES HAVE TO BE REPLACED AT REGULAR

INTERVALS, THUS ADDING TO THE COST OF THE
EXTRACTION PROCESS
 Extraction
In a newer process, purification of the oxide is of
much less importance
Aluminium chloride vapour is passed through the
fused oxide at about 1300 K.
2Al2O3 + 2AlCl3 → 6AlCl + 3O2
 Thealuminium monochloride vapour is unstable when cooled
and disproportionates below 1100 K thus: 3AlCl → AlCl3 +
2Al
 The aluminium trichloride is then re-cycled through the
 Extraction
Boron can be obtained by heating boron trioxide
with magnesium:
B2O3 + 3Mg → 2B + 3MgO
The boron obtained is an amorphous powder.
It can be obtained in the crystalline state by
reducing the vapour of boron tribromide with
hydrogen,
either in an electric arc.
 Extraction
 Or in contact with an electrically-heated
tungsten filament:
2BBr3 + 3H2 → 2B + 6HBr.
Pure boron in the form of a thin film can also be
obtained by heating diborane to 1000 K:
B2H6 → 2B + 3H2
Amorphous boron has not been obtained in the
pure state.
 Extraction
Crystallineboron is a black powder,
Extremely hard,
With a metallic appearance
However, it has very low electrical conductivity.
 SIMPLE COMPOUNDS OF BORON AND ALUMINIUM
It must be noted that the chemical properties of
boron and its compounds are different from those
of its congeners.
Trends in properties of the compounds.
With hydrogen
Boron forms an elaborate range of neutral and
anionic hydrides called BORANES.
They have cage-like structures.
 COMPOUNDS OF BORON WITH HYDROGEN
Synthetic hydride of boron are called boranes.
They have the generic formula BxHy.
Boranes are electron deficient, hence are
highly reactive with respect to electron-pair
donors.
The first three ionization energies of boron,
are much too high to allow formation of
compounds containing the B ion.
3+
 COMPOUNDS OF BORON WITH HYDROGEN
Thus, all compounds of boron are covalently
bonded.
Boranes are electron-deficient compounds.
Two types of bonds in boranes are well known
• the regular two-center 2e- bond (2c-2e)
• a three-center 2e- bond (3c-2e)
 COMPOUNDS OF BORON WITH HYDROGEN
The simplest member of this group is called
diborane.
3-center 2-electron B-H-B hydrogen bridges
3-center 2-electron B-B-B bonds
2-center 2-electron bonds (in B-B, B-H)
 PREPARATION OF BORON HYDRIDES
Itis prepared in the laboratory by metathesis of
boron trihalide with either LiAlH4 or NaBH4 in
ether or by reduction.
3NaBH4 + 4BF3 → 2B2H6(g) + 3NaBF4
3LiAlH4 + 4BCl3 → 2B2H6(g) + 3LiAlCl4

REDUCTION METHOD
BCl3 + 3H2 → 1/2B2H6(g) + 3HCl (Reduction BCl 3)
 PROPERTIES OF BORON HYDRIDE
 Allthe boron hydrides are flammable.
 The lighter boranes react spontaneously in air given
boron oxide and steam.
 B2H6(g) + 3O2(g) → B2O3(s) + 3H2O(g)
 B2H6(g) + 3O2 → 2B(OH)3(g)
 With water
 B2H6(g) + 6H2O(l) → 2B(OH)3(aq) + 6H2(g)
 The reactions signify that lower boranes are pyrophoric
in air and react violently with water.
 COMPOUNDS OF ALUMINIUM WITH HYDROGEN

The hydrides of aluminium

Aluminium hydride has the formula AlH3.
PREPARATION
Aluminium hydride is prepared by reacting
lithium aluminium hydride with aluminium
trichloride.
3LiAlH4 + AlCl3 → 4AlH3 + 3LiCl
2LiAlH4 + H2SO4 → 2AlH3 + Li2SO4 + 2H2
 SIMPLE COMPOUNDS OF BORON AND ALUMINIUM

PROPERTIES
Aluminium hydride is not spontaneously
flammable.
Aluminum hydride is a pyrophoric solid.
It is highly reactive, similar to lithium
aluminium hydride.
Aluminium hydride decomposes in air and
water.
 USES OF BORON HYDRIDE AND ALUMINIUM HYDRIDE
 The main chemical application of boranes is the
hydroboration reaction.
 Neutron capture therapy of cancer is a promising
development.
 Aluminium hydride is mainly used for the reduction of
functional groups.
 Aluminum hydride converts aldehydes, ketones,
carboxylic acids, anhydrides, esters to their
corresponding alcohols.
 SIMPLE COMPOUNDS OF BORON AND ALUMINIUM

WITH OXYGEN
Aluminium will burn in oxygen with a brilliant
white flame to form the trioxide alumnium(III)
oxide, Al2O3.
4Al(s) + 3O2(l) → 2Al2O3(s)
B2O3 (Sesquioxide) is the most important oxide of
boron. It is prepared by dehydration of boric acid.
2B(OH)3(s) → B2O3(s) + 3H2O(g)
 Boron Compounds and Oxygen
B(OH)3 + 2H2O B(OH)4+ + H3O-
or
H3BO3
OH
OH -

OH B

B
OH OH
OH OH
Tetrahedral metaborate ion
Plane triangle
 Reaction of aluminium with the halogens

Aluminium metal reacts vigorously with all

the halogens to form aluminium halides.
It reacts with chlorine, Cl2 to form
aluminium(III) chloride, AlCl3
2Al(s) + 3Cl2(l) → 2AlCl3(s)
2Al(s) + 3Br2(l) → Al2Br6(s)
2Al(s) + 3I2(l) → Al2I6(s)
 Reaction of boron with the halogens

Boron trihalides are useful Lewis acids, with

BCl3 > BF3
All the boron trihalides except BI3 may be
prepared by direct reaction between the
elements.
B2O3(s) + 6H2SO4(aq) + 3CaF2(s) →
2BF3(g) + [H3O][HSO4] + 3CaSO4(s)
 REACTIONS OF THE ELEMENTS
The reactions of the heavier group 13 elements is
different from the first member of the group.
Aluminium readily oxidizes in air
It dissolves in dilute mineral acids but is
passivated by concentrated HNO3.
Aluminium reacts with aqueous NaOH or KOH
liberating H2
 REACTIONS OF THE ELEMENTS WITH ACIDS
Other members of the group react as typical
metals and evolve hydrogen.
Aluminium, gallium and indium are oxidised to the
+ 3 oxidation state
2Al + 2MOH + 6H2O → 2M[Al(OH)4] + H2
Al + 3H2SO4 → Al(SO4)3 + 3H2
 REACTIONS OF THE ELEMENTS WITH ACIDS
2M +6H + → 2M3+ + 3H2
However, thallium is oxidized to the
+ 1 oxidation state: 2Tl + 2H+ → 2Tl+ + H2
Strong oxidizing acids- hot concentrated
sulphuric acid and nitric acid, attack finely
divided boron to give boric acid H3BO3.
The metal is oxidised while the acid is
reduced
 REACTIONS OF THE ELEMENTS WITH ACIDS
Bulk aluminum is rendered "passive' by both dilute
and concentrated nitric acid and no action occurs.
The passivity is due to the formation of an
impervious (corrosion resistant) oxide layer.
However, finely divided aluminum does dissolve
slowly when heated in concentrated nitric acid.
 Reactions of the Alkalis (Sodium Hydroxide)
Amorphous boron and the amphoteric elements,
aluminum and gallium, are attacked by aqueous
solutions of sodium hydroxide
 hydrogen is liberated
 Reactions of the Elements with Water
Neither boron nor aluminum reacts with water at
room temperature
But both react with steam at red heat liberating
hydrogen
2B + 6H2O → 2H3BO3 + 3H2
2Al + 3H2O → Al2O3 + 3H2
For aluminium, the inertness to water is due to
the formation of an unreactive layer of oxide on
the metal surface.
 Reactions of the Elements with
Air
In addition to oxide formation, boron and
aluminum react at high temperature with the
nitrogen in the air to form nitrides (BN and
AlN).
 USES OF THE ELEMENTS

Corundum (alumina) and emery (corundum

mixed with the iron oxides magnetite and
haematite) are extremely hard and are used
as abrasives
 USES OF THE ELEMENTS

Diamond is the only naturally occurring

mineral harder than corundum.
 Borosilicate glass has a high refractive index
and is suitable for optical lenses.
 USES OF THE ELEMENTS
Borax has been used in pottery glazes for
many centuries and remains in use in the
ceramics industry.
 Amorphous boron is used in pyrotechnics,
giving a characteristic green colour when it
burns.
 USES OF THE ELEMENTS

Gallium and indium phosphides, arsenides

and antimonides have important applications
in the semiconductor industry
 USES OF THE ELEMENTS

They are used as transistor materials and in

light-emitting diodes (LEDs) in, for example,
pocket calculators