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Detailed Discussions On Aluminium

ChemistryThe p-Block Elements: Group 13 & 14For NEET aspirants

Aluminium is the most abundant metal in the earth's crust ( by weight) and the third most abundant element overall, after oxygen and silicon. Its silvery-white metallic look, low density ( g cm), excellent electrical conductivity and remarkable resistance to corrosion - thanks to a self-repairing oxide film - make it central to modern industry. This concept covers aluminium's occurrence, its two-stage extraction from bauxite (Bayer's process followed by Hall-Heroult electrolysis), its physical and chemical properties including the important amphoteric behaviour, and its key compounds such as alumina, aluminium chloride and alums.

Key Formulas & Facts - Quick Reference
  1. Chief ore: bauxite, ; abundance: ; density: g cm; m.p.: K
  2. Bayer's process: ; then
  3. Hall-Heroult (in molten cryolite ): cathode ; anode
  4. Amphoteric nature: and
  5. Thermite reaction: ( kJ mol)
  6. dimer: , with two bridging Cl atoms
  7. Potash alum: or

1. Occurrence and Ores

Aluminium is far too reactive to occur free in nature. It is always found combined with oxygen or silicon. The commercially important ores are:

  • Bauxite: - the principal ore worldwide.
  • Cryolite: - used both as an ore and as the electrolyte solvent in Hall-Heroult.
  • Corundum: (anhydrous crystalline) - gemstones (ruby with , sapphire with ).
  • Feldspar:
  • Mica:
  • Kaolinite (china clay):

2. Extraction: Stage I - Purification of Bauxite (Bayer's Process)

Bauxite typically contains iron oxide (), silica () and titanium dioxide () as impurities. The Bayer's process exploits the amphoteric nature of to separate it from the basic and the acidic .

  1. Digestion: Crushed bauxite is treated with concentrated (about ) at K and bar in an autoclave. and dissolve as sodium aluminate and sodium silicate; and remain insoluble and are filtered off as red mud.

  2. Precipitation: The clear filtrate is cooled, diluted and seeded with a small quantity of freshly precipitated . This induces to crystallise out slowly, while sodium silicate stays in solution.
  3. Calcination: The washed is heated to K to give pure alumina.
Bayer's process flow chart for purification of bauxite A six stage flow chart. Bauxite is digested with sodium hydroxide under pressure, filtered to remove red mud, seeded to precipitate aluminium hydroxide, and calcined at 1473 kelvin to give pure alumina. Bayer's process - purification of bauxite Bauxite ore + NaOH (45%) Digester 473-523 K, 36 bar Na[Al(OH)₄] solution Filter removes Fe₂O₃, TiO₂ as red mud Precipitator seeded with Al(OH)₃ Al(OH)₃ ↓ Calciner 1473 K Al(OH)₃ → Al₂O₃ Pure Al₂O₃ (alumina) Basic Fe₂O₃ and acidic TiO₂ stay undissolved; only amphoteric Al₂O₃ dissolves in NaOH.
Figure 1: Flow diagram of Bayer's process. Amphoteric dissolves in hot concentrated while (basic) and (acidic) do not, so the impurities are filtered out as red mud.
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Why seeding works: the sodium aluminate solution from the digester is supersaturated in after cooling and dilution - but nucleation is very slow. Adding a small amount of pre-formed crystals provides growth sites, so the excess ion crystallises out on them.

Meanwhile the sodium silicate (also present in solution) stays in solution because it is not supersaturated at these conditions. This is the key separation trick of the Bayer's process: seed-selective precipitation of aluminate ahead of silicate.

3. Extraction: Stage II - Hall-Heroult Electrolysis

Pure alumina has a very high melting point ( K), which makes direct electrolysis impractical. Charles Hall and Paul Heroult independently discovered in that alumina dissolves readily in molten cryolite () at only K, giving a highly conducting melt suitable for electrolysis.

Ellingham style comparison of aluminium and carbon oxidation lines A free energy versus temperature plot. The aluminium oxidation line is far more negative than the carbon to carbon monoxide line and the two only cross near 2300 kelvin, showing carbon reduction of alumina is not practical. Why carbon cannot reduce alumina in practice -1000 -800 -600 -400 -200 500 1000 1500 2000 Temperature / K ΔG° / kJ per mol O₂ 4/3 Al + O₂ → 2/3 Al₂O₃ 2C + O₂ → 2CO cross-over ~2300 K Below ~2300 K the Al line lies lower, so carbon cannot pull oxygen away from Al₂O₃. Aluminium is therefore extracted by electrolysis, not by carbon reduction.
Figure 2: An Ellingham-style comparison. The line lies below the line until about K, so carbon cannot reduce alumina at any workable furnace temperature. This is exactly why aluminium is won electrolytically in the Hall-Heroult cell rather than in a blast furnace.

Cell and electrolyte

  • Cell: a steel tank lined internally with graphite (which acts as the cathode).
  • Anodes: a set of graphite rods dipped into the melt from above.
  • Electrolyte: molten cryolite () + fluorite () + () + alumina (). further lowers the melting point of the mixture and improves conductivity.
  • Voltage: V; current density A cm; temperature K.
Hall Heroult electrolytic cell for aluminium extraction Cross-section of a Hall Heroult cell. A steel shell with a carbon lining acts as the cathode, graphite anodes dip into a molten cryolite and alumina bath, molten aluminium collects at the bottom and carbon dioxide escapes at the anodes. Hall-Heroult cell for aluminium DC 5-6 V + − Steel shell Carbon lining (cathode) Molten cryolite Na₃AlF₆ + Al₂O₃ + AlF₃ + CaF₂ (electrolyte, ~1225 K) Molten Al (d = 2.7) collects at the bottom Graphite anodes (+) CO₂ / CO tap off Cathode: Al³⁺ + 3e⁻ → Al(l) Anode: C + 2O²⁻ → CO₂ + 4e⁻
Figure 3: The Hall-Heroult cell. Alumina dissolved in molten cryolite is electrolysed between graphite anodes and a carbon-lined cathode. Molten Al ( g cm) is denser than the melt () so it collects at the bottom and is tapped off; the anodes are slowly burnt away as and .

Electrode reactions

In the melt, alumina ionises approximately as:

  • Cathode:
  • Anode: , but the liberated oxygen immediately attacks the hot graphite anode: and .
Because the anode is consumed as and , it must be replaced every few weeks. Modern plants use pre-baked or Soderberg-type carbon anodes.

4. Physical and Chemical Properties

Physical properties

  • Silvery-white, malleable and ductile metal; can be beaten into very thin foils.
  • Density g cm (light metal); m.p. K; b.p. K.
  • Excellent conductor of heat and electricity ( of copper on volume basis but on mass basis).
  • Face-centred cubic (FCC) lattice, giving it high ductility.

Chemical properties

(i) Reaction with air: Pure Al is not attacked by dry air, but in moist air a thin, impervious film of ( cm) forms and protects the underlying metal from further corrosion. On strong heating in air, aluminium powder burns with a dazzling flame:

   kJ mol

(ii) Reaction with water: No reaction with cold or hot water because of the oxide film. If the film is removed (by amalgamation with Hg), Al reacts even with cold water:

(iii) Reaction with dilute acids: Al liberates from dilute and dilute :

(iv) Reaction with concentrated : Al becomes passive due to formation of a very thick oxide layer. Hence concentrated is transported in aluminium containers.

Protective oxide film on aluminium and passivation by concentrated nitric acid Two panels each showing a block of aluminium metal covered by a surface oxide layer with reagents arriving from above. In moist air the film is very thin; with concentrated nitric acid it becomes much thicker and the metal is passivated. The self-repairing oxide film on aluminium In moist air Al metal O₂ / H₂O Al₂O₃ film, ~10⁻5 cm Thin, impervious, self-repairing With conc. HNO₃ Al metal conc. HNO₃ thick passive film Metal goes passive - no further attack This is why aluminium resists corrosion, and why conc. HNO₃ is transported in aluminium tankers.
Figure 4: Aluminium owes its corrosion resistance to a thin, tightly adherent film (about cm) that re-forms the instant it is scratched. Concentrated thickens this film into an impervious layer, so the metal becomes passive instead of dissolving.

(v) Reaction with alkalis (amphoteric behaviour): Al reacts with hot solution to form sodium aluminate and :

(older way of writing: )

Amphoteric behaviour of aluminium hydroxide Aluminium hydroxide in the centre with two routes. Towards hydrochloric acid it acts as a base giving aluminium chloride; towards sodium hydroxide it acts as an acid giving sodium aluminate. Amphoteric behaviour of Al(OH)₃ Al(OH)₃ amphoteric hydroxide + 3 HCl (as base) AlCl₃ + 3H₂O salt + NaOH (as acid) Na[Al(OH)₄] sodium aluminate Al³⁺ is small and strongly polarising, so the O-H bond can break either way. This dual character is exactly what makes Bayer's separation possible.
Figure 5: is amphoteric. It acts as a base towards acids (giving ) and as an acid towards strong alkalis (giving sodium aluminate). The same dual character in is what lets Bayer's process strip it away from basic and acidic .
Why amphoteric? is on the borderline between metal and non-metal. Its ion is small and highly polarising, so and can react with both acids (as bases) and alkalis (as acids). This is exactly what makes Bayer's process possible.

(vi) Reaction with halogens:

  ()

(vii) Reduction of metal oxides (thermite reaction): Al is a strong reducing agent because is very stable ( kJ mol). Aluminothermic reduction is used to produce metals like Cr, Mn from their oxides:

  ( kJ mol)

Thermite process for on-site welding of railway tracks A crucible of aluminium powder and iron oxide ignited by a magnesium ribbon pours molten iron down into the gap between two railway rails, where it solidifies into a weld. Thermite welding of railway tracks 2Al + Fe₂O₃ → 2Fe + Al₂O₃    ΔH = −852 kJ mol⁻¹ Al powder + Fe₂O₃ (thermite mixture) finely divided powders Mg ribbon (ignitor) molten Fe (over 2500 K) Rail 1 Rail 2 gap filled by molten iron, which solidifies into a strong joint
Figure 6: The thermite (aluminothermic) process for on-site welding of broken rails. A ribbon ignites the mixture; the reaction is so exothermic ( kJ mol) that the iron is produced molten and runs straight into the gap. The same reduction gives Cr, Mn and V from their oxides.
Solved Example 1
Aluminium vessels should not be washed with strong washing soda solution. Explain.
Solution:

Strong washing soda () is a strong alkali in solution because it hydrolyses to give . Aluminium is amphoteric and reacts with to give sodium aluminate and hydrogen gas: . This dissolves the protective oxide film and eats into the vessel, releasing and causing pitting. That is why aluminium cookware carries a warning against alkaline detergents.

5. Uses of Aluminium and its Alloys

  • Household utensils, cans and cooking foil (light, non-toxic, corrosion-resistant).
  • Transmission cables for electricity - lighter and cheaper than copper for the same current-carrying capacity.
  • Aircraft and automobile parts (mostly as duralumin: ).
  • Window frames, doors, roofing (via magnalium: ).
  • Aluminothermic process for on-site welding and for extraction of Cr, Mn, V, Mo.
  • Silvery paint (aluminium powder mixed with linseed oil) for radiators and boilers.
  • Wrappers for chocolates, medicines and cigarettes (Al foil).

6. Important Compounds of Aluminium

6.1 Aluminium oxide (alumina),

Alumina exists in several crystalline forms; the most common are - (corundum, very hard, used as an abrasive) and - (a porous form used as a catalyst support and drying agent).

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Corundum coloured by trace impurities gives gemstones:

GemstoneColourImpurity ion
RubyRed
SapphireBlue + (charge-transfer)
TopazYellow
EmeraldGreen (in beryl matrix, not corundum)
AmethystViolet (in quartz)

is amphoteric:

6.2 Aluminium chloride,

Anhydrous is a white sublimable solid ( K). In the gas phase and in non-polar solvents it exists as the dimer , in which two Cl atoms bridge between two Al centres by donating lone pairs, completing the octet on both Al atoms.

Dimeric structure of aluminium chloride Al2Cl6 Two aluminium atoms bridged by two chlorine atoms in a four membered ring, each aluminium also carrying two terminal chlorines. The bridging chlorines donate lone pairs so both aluminium atoms complete their octet. Al₂Cl₆ dimer (vapour and non-polar solvent) Al Al Cl Cl Cl Cl Cl Cl 118° 79° Solid lines = normal covalent Al-Cl bonds; dashed = coordinate (dative) Cl → Al bonds Each Al reaches an octet and is sp³ hybridised; the Al₂Cl₂ ring is planar
Figure 7: has a four-membered ring. Each bridging Cl donates a lone pair coordinately (dashed) so both Al atoms complete their octet and become . Bond angles: -- and --.

Preparation: anhydrous is made by passing dry over red-hot Al or over a hot mixture of and coke:

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Industrial route from bauxite (without pure Al metal): a mixture of alumina and coke is heated in a stream of chlorine gas at K. Carbon acts as a reductant, removing the oxygen as :

This is the cheaper industrial route for large-scale anhydrous production. The gaseous is condensed to a white sublimable solid.

Hydrolysis of hydrated salt: the hydrated salt cannot be dehydrated by direct heating - it hydrolyses instead:

; then

Uses: is a strong Lewis acid and the classical catalyst for the Friedel-Crafts alkylation and acylation of aromatic compounds.

6.3 Aluminium hydroxide,

Formed as a gelatinous white precipitate when is added to an aluminium salt solution:

It is amphoteric:

Important: (weak base) does not dissolve , so ammonia is used to precipitate Al selectively in the presence of other cations that dissolve in .

Separation of aluminium and zinc ions using sodium hydroxide or ammonia A branching chart. With excess sodium hydroxide both aluminium and zinc hydroxides dissolve. With excess ammonia only zinc dissolves as an ammine complex while aluminium hydroxide remains as a precipitate. Separating Al³⁺ from Zn²⁺: choice of base matters Mixture of Al³⁺ + Zn²⁺ in solution excess NaOH excess NH₄OH Both dissolve Al → [Al(OH)₄]⁻ Zn → [Zn(OH)₄]²⁻ no separation They part company Al(OH)₃ stays undissolved ↓ Zn → [Zn(NH₃)₄]²⁺ (soluble) filter to collect Al(OH)₃ Al(OH)₃ dissolves in strong alkali but NOT in NH₄OH, because it forms no ammine complex. Zn²⁺ does form one, so ammonia is the reagent that separates the two ions.
Figure 8: Both and dissolve in excess , so a strong alkali cannot tell them apart. With excess only zinc dissolves (as the ammine complex ) while stays behind as a precipitate, which is the standard way of separating the two in qualitative analysis.

6.4 Alums

An alum is a double sulphate of the general formula , where is a monovalent cation (Na, K, NH, Tl) and is a trivalent cation (Al, Cr, Fe).

The most familiar is potash alum: , or equivalently .

Formula anatomy of potash alum The potash alum formula split into four parts: a monovalent cation sulphate, a trivalent cation sulphate, the shared sulphate anion and twenty four water molecules of crystallisation. Potash alum: K₂SO₄ · Al₂(SO₄)₃ · 24H₂O simplified: KAl(SO₄)₂ · 12H₂O K₂SO₄ Monovalent cation M¹ = Na, K, NH₄, Tl Al₂(SO₄)₃ Trivalent cation M³ = Al, Cr, Fe SO₄²⁻ Shared anion 4 per formula unit 24 H₂O Water of hydration always 24 in an alum · · · Swap M¹ or M³ and it is still an alum: sodium alum, ammonium alum, chrome alum. All alums are isomorphous - they crystallise in the same octahedral shape. Uses: water purification, paper sizing, mordant in dyeing, styptic to stop bleeding.
Figure 9: Anatomy of the alum formula. Change (K to Na, , Tl) or (Al to Cr, Fe) and the compound is still an alum. Common examples are sodium alum, ammonium alum and chrome alum ().

Alums are isomorphous (they crystallise with the same octahedral shape). Uses include: purification of water (as a coagulant of colloidal impurities), sizing of paper, mordanting in dyeing, and as a styptic (to stop bleeding from minor cuts).

Solved Example 2
Anhydrous is covalent while is ionic. Justify.
Solution:

Apply Fajans' rules. is small and carries a charge, so its polarising power is very high. The ion is small and hard to polarise, so - interactions retain a strongly ionic character and is a high-melting ionic solid ( K). The ion is much larger and more polarisable, so heavily distorts its electron cloud, producing significant covalent character. This is why is a low-melting, sublimable solid that exists as covalent dimers in the vapour phase.

Fajans rules comparing ionic aluminium fluoride with covalent aluminium chloride Two panels. In aluminium fluoride the small fluoride ion keeps a spherical electron cloud and the bond stays ionic. In aluminium chloride the large chloride cloud is pulled towards the aluminium ion, giving covalent character. Fajans' rules: why AlF₃ is ionic but AlCl₃ is covalent AlF₃ F Al Al³⁺ small, +3 F⁻ small, hard Electron cloud barely distorted ionic solid, m.p. 1563 K AlCl₃ Cl Al Al³⁺ small, +3 Cl⁻ large, soft Cloud pulled towards Al³⁺ covalent, sublimes at 465 K Greater polarisation of the anion → more covalent character. That is Fajans' rule.
Figure 10: Fajans' rules in picture form. is small and triply charged, so it polarises strongly. is small and hard, so stays ionic and melts at K; is large and soft, so its cloud is pulled towards , giving covalent that sublimes at K and exists as in the vapour.
Solved Example 3
Why is cryolite added to alumina in the Hall-Heroult process even though it is not the source of aluminium?
Solution:

Pure melts at K, which is far too high for practical electrolysis (energy cost, corrosion, container problems). Molten cryolite () dissolves and forms a conducting melt at around K, roughly K lower than pure alumina's melting point. Cryolite also improves electrical conductivity of the melt (alumina alone is a poor conductor) and lowers the density of the electrolyte enough that molten Al () sinks to the bottom and can be tapped off. The added further lowers the operating temperature.

Common Mistakes to Avoid

Watch out
  • Do not confuse Bayer's process (purification of bauxite by NaOH) with the Hall-Heroult process (electrolysis of pure alumina in molten cryolite). Both are needed - Bayer's gives pure , Hall-Heroult reduces it to metal.
  • Cryolite is not decomposed by the current in the Hall-Heroult cell; it acts only as a solvent for alumina.
  • Anhydrous cannot be obtained by heating hydrated - hydrolysis occurs instead giving and . Use passage of dry over Al metal.
  • dissolves in (a strong base) but not in (weak base). Use this to separate from - both hydroxides dissolve in but only dissolves in excess .
  • In the aluminate anion, the formula is or (older). Never write - that is unbalanced.
  • Concentrated passivates Al by thickening the oxide film. Do not write a "no reaction" - write "passivation".

Frequently Asked Questions

Q1. What are the main steps in the extraction of aluminium?

Aluminium is extracted from bauxite in two stages. Stage I - Bayer's process: bauxite is digested with hot concentrated at K, filtered to remove and , and the aluminate solution is seeded with to precipitate pure aluminium hydroxide, which is calcined at K to give pure alumina. Stage II - Hall-Heroult process: pure is dissolved in molten cryolite () at K and electrolysed with graphite electrodes to yield molten aluminium at the cathode.

Q2. Why is molten cryolite added to alumina in the Hall-Heroult process?

Pure alumina melts at K, which is impractically high. Molten cryolite () dissolves and forms a highly conducting melt at only K. Small amounts of further lower the melting point and improves conductivity. Cryolite itself is not reduced - it is just the solvent.

Q3. Why does aluminium show amphoteric behaviour?

Aluminium sits at the borderline between metals and non-metals. Its small, highly-charged ion has strong polarising power, giving its oxide and hydroxide dual character: they behave as bases towards strong acids () and as acids towards strong alkalis (). This amphoteric nature is exploited in Bayer's process to separate from basic and acidic .

Q4. Why does aluminium not react with concentrated nitric acid?

Concentrated is a strong oxidising acid. When it contacts Al, it very quickly thickens the natural surface oxide layer into an impervious coating that prevents any further attack. This state is called passivation. Because of passivation, concentrated is safely transported in aluminium tankers.

Q5. What is the thermite reaction and where is it used?

The thermite reaction is the reduction of a metal oxide by aluminium powder: ( kJ mol). The heat released melts the iron produced. The classic application is on-site welding of broken railway tracks - the molten iron flows into the gap and solidifies as a strong joint. The same aluminothermic reduction is used industrially to extract Cr, Mn and V from their oxides.

Q6. Why is a dimer while is a monomer?

In , boron's empty orbital is stabilised by - back-donation from Cl lone pairs, and BCl3 is trigonal planar and monomeric. In , no effective back-bonding to -Al is possible from Cl, so Al is genuinely electron-deficient. Two units therefore dimerise: two Cl atoms bridge across, donating lone pairs coordinately to both Al centres and completing the octet.

Q7. What is an alum and what are alums used for?

An alum is a double sulphate of a monovalent metal (: Na, K, NH, Tl) and a trivalent metal (: Al, Cr, Fe) with molecules of water: . Potash alum is the most common. Uses include water purification (coagulating colloidal impurities), sizing of paper, mordanting in dyeing and as a styptic to stop bleeding from small cuts.

Q8. Why is aluminium used to make electricity transmission cables even though copper is a better conductor?

On a mass basis (per kilogram), aluminium actually conducts electricity about twice as well as copper because it is much less dense. For transmission lines, weight matters - heavier cables need stronger, more expensive towers. Aluminium is also much cheaper and is corrosion-resistant. So even though copper wins on conductivity per unit volume, aluminium wins on cost and weight for long-distance transmission.

Q9. Which impurities give ruby and sapphire their colours?

Both ruby and sapphire are corundum (-) with trace impurity ions. Ruby gets its red colour from substituting for in the lattice. Sapphire's characteristic blue arises from a metal-to-metal charge transfer between and impurity ions, which absorbs red-orange light and leaves the transmitted light blue.

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