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❖Boron and aluminium chemistry : oxide, hydride, halide,

❖Aluminium metal, alloys and alumina
❖Extraction of aluminium
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GROUP 13 ELEMENTS : B, Al, Ga, In, Tl

❖ Many of the compounds are on the borderline of ionic-covalent character

❖Boron is metalloid & the rest are metals (poor metal or post-transition
metal)
❖ Elements exist in two oxidation state (+1 and +3)
❖ Boron
-pure boron is a little-used dark (grey) powder
-non-metal with a covalent network structure
-optical characteristics : poor conductor of electricity at room temperature,
good conductor at high temperature
-does not form binary ionic compounds and is unreactive toward oxygen gas
and water
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HYDRIDE
❑Boron hydride
-boranes : the simplest of these is not BH3 as expected but its dimer B2H6
-diborane: the simplest of the boranes is diborane(6) or B2H6. It is the only stable
borane with 2 boron atoms and is frequently just called diborane
-structure of diborane :

OXIDE, HYDROXIDE
❑Boron trioxide, Boric acid : B(OH)3 or H3BO3
-boron trioxide is more easily obtained by heating boric acid to red heat :

-it is a solid of glassy appearance, amphoteric, hygroscopic and combining slowly

with water to form boric acid
-it forms various salts : borax
-is an acidic oxide and an insoluble white solid with a very high boiling point
(>2000K) because of its extended covalently-bonded network structure and insoluble
in water
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-B(OH)3 acts as an acid by accepting a pair of electrons from incoming OH - ion

-negative end of hydroxide (oxygen atom) attacks partially positive boron atom
to form fourth B-OH bond.
-boron atom – sp3 hybridization.
-only one OH- group is accepted – this compound as monobasic and not
tribasic
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❖ Aluminium
-hard, durable, strong, silvery-white metal, soft and lightweight metal
-aluminium is remarkable for its ability to resist corrosion-aluminium is
remarkable for its ability to resist corrosion (due to the phenomenon
of passivation) and its light weight.
-passivation is the spontaneous formation of a hard non-reactive surface film
that inhibits further corrosion. This layer is usually an oxide or nitride that is a
few atoms thick.
-a thicker layer of oxide can be placed on the aluminium or aluminium alloy
by an electrolytic process – anodization (to enhanced the thickness)
-thicker layer of oxide – will absorb colored dyes – in pleasant-appearing
product used in furniture & awnings
-aluminium foil : early purpose to protect cigarettes and hard candies from
moisture. Now – food was sold in attractive aluminium packaging.
-aluminium has close-packed metallic structure but it is on the borderline
between ionic and covalent character in its compounds
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•Why is aluminium resistant to air and Al Al Al Al Al Al

water, even though it is very
electropositive? Al Al Al Al Al Al

Al Al Al Al Al Al
- Any exposed surface of aluminium
metal rapidly reacts with oxygen to
form aluminium oxide, Al2O3

O O

- Oxide layer is formed on the

surface : a tough film, hard,
impermeable thickness between 10-4
O2- O2- O2- O2- O2- O2-
– 10-6 mm
Al Al Al Al Al Al
- Protects the layers of aluminium
atoms underneath Al Al Al Al Al Al
 OXIDE
• Aluminium oxide is an amphoteric oxide is an amphoteric oxide of
aluminium
• Aluminium oxide can act either as an acid or a base.
In a strongly acidic environment, these oxides will act as bases;
whereas in a strongly basic environment, these oxides will act as
acids.
• Examples:
• Aluminum oxide
– in acid: Al2O3 + 6HCl → 2AlCl3 + 3H2O
– in base: Al2O3 + 2NaOH + 3H2O → 2NaAl(OH)4

❖ Alloy
-To improve the structural properties, aluminium is mixed with various metals :
copper, silicon, magnesium, manganese and zinc.
-Much lighter and more corrosion resistant than plain carbon steel, but not
quite as corrosion resistant as pure aluminium.
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❖ Alumina
-pure form of Al2O3 – white solid
-anhydrous Al2O3 : α- Al2O3 & γ- Al2O3
-the aluminas used for chromatography and conditioned to different
reactivities are γ- Al2O3

-large quantities of α- Al2O3 are used in industry as a support material for

heterogeneous catalysts

-α- Al2O3 occurs naturally as corundum : abrasive in products such as

grinding wheels, sandpaper, toothpaste

-Corundum-Corundum is the naturally occurring crystalline-Corundum is

the naturally occurring crystalline form of aluminium oxide. Rubies-
Corundum is the naturally occurring crystalline form of aluminium oxide.
Rubies and sapphires are gem-quality forms of corundum with their
characteristic colors due to trace impurities in the corundum structure.
-Impure crystalline forms of Al2O 3 are valuable – gems : red ruby (Cr3+), blue
sapphire (Fe2+ , Fe3+ , Ti4+ ), green oriental emerald (Cr3+ , Ti3+ ), violet
3+ 4+ 3+
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HALIDE
❑ Aluminium chloride
-dimer molecule Al2Cl6

-solid aluminium chloride sublime at 180ºC and the structure will

change to Al2Cl6 dimer molecule exist as vapor until 400ºC. Then,
Al2Cl6 will dissociate to AlCl3 (trigonal planar molecule)
-preparation of aluminium chloride:
1) Passing hydrogen chloride or chlorine over hot aluminium
2) Passing chlorine over heated aluminium oxide and carbon
(industrially)
-chloride ion is polarized by small positive aluminium ion and the
bonding in the solid is intermediate between covalent and ionic
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HYDRIDE
❑ Aluminium hydride
-AlH3, is a chemical reagent used as a reducing agent, is a chemical
reagent used as a reducing agent. It is used in hydroalumination of
alkynes, is a chemical reagent used as a reducing agent. It is used in
hydroalumination of alkynes, allylic rearrangements, and storing hydrogen
in hydrogen-fuel vehicles.
-It is a colourless polymeric solid, (AlH3)n. The molecular AlH3 species are
not stable. Monomeric AlH3 has been isolated at low temperature in a solid
noble gas matrix and shown to be planar
-the dimer, Al2H6, has been isolated in solid hydrogen and is isostructural
with diborane
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GROUP 13 ELEMENTS : B, Al, Ga, In, Tl

Al

▪Hall-Héroult process is the major industrial process for the production

of aluminium
▪Aluminium metal is obtained from bauxite (Al2O3.nH2O) – an ore
of aluminium (impure aluminium oxide)
▪Useful compound in bauxite – aluminium oxide
▪The material requires purification from impurities such as silica, oxides
of iron and titanium oxide.
▪Ore is first converted into pure aluminium oxide by the Bayer
Process, and this is then electrolysed in solution in molten cryolite
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Cathode / carbon Anode / carbon

Aluminium (l) CO2 (g)

Electrolysis 900ºC
Aluminium oxide (l) Na3AlF6 (cryolite)
+ Pure aluminium oxide (s)
Cryolite heat
Heat

Sodium silicate (aq) + Aluminium hydroxide (s)

CO2

concentrated NaOH (aq) Sodium aluminate (aq)

Bauxite (s) +
heat Sodium silicate (aq)
Filter
Ferum (III) oxide + Titanium (IV) oxide
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1) Finely powdered product is dissolved in concentrated caustic soda solution &

heated to about 160°C under 35 atm.

aluminate

silicate

2)Undissolved impurities (Fe2O3 and TiO2) are filtered off. All of these solids are
separated from the aluminate solution by filtration. They form a red mud
3)Silica dissolve as sodium silicate and aluminium oxide reacts to form sodium
aluminate in solution - filtrate
4)Filtrate is diluted with H2O and CO2 (hydrolysis of dissolved aluminate) to produce
precipitate of aluminium hydroxide

5) Hydroxide is filtered off, washed, dried and heated strongly to leave pure
aluminum oxide
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❖ To extract aluminium metal from aluminium oxide - difficult to remove

aluminium from oxygen in the oxides

❖The aluminium oxide is dissolved in molten cryolite,

Na3AlF6 (sodium aluminium fluoride) to lower the temperature needed to
melt the oxide.

❖Mixture is electrolysed, molten aluminium forms at the negative electrode

(cathode): Al3+ + 3e− Al

The Al3+ ions are reduced at the negative electrode (cathode). They receive
electrons and form aluminium atoms.

At the positive electrodes (anodes), the oxide ions (O2−) are oxidized to form
oxygen gas (O2) :
2O2− − 4e− O2
The oxygen produced reacts with the carbon anodes. This makes carbon
dioxide gas and, in effect, the anodes are burned away. These have to be
replaced frequently in the cells.

C(g) + O2(g) CO2(g)

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❖ Gallium, Indium and Thallium

-gallium : silvery, glass-like, soft metal

-indium : very soft, silvery-white metal with a brilliant luster

-thallium : soft, silvery metal, but it soon develops a bluish-grey tinge as

the oxide forms if it is exposed to the air