Metals and Their Compounds
Metals are elements that ionize by losing electrons. They possess unique characteristics that differentiate them from non-metals. Their physical properties depend on the arrangement of atoms or molecules in a crystal lattice, and the type of bonding present in different states of matter. Chemically, the behavior of metals is largely determined by the number of valence electrons in their atoms. Over 75% of known elements are classified as metals.
Physical Properties of Metals
- High melting and boiling points
- Shiny (metallic luster)
- Malleable (can be hammered into sheets)
- Hard but not brittle; high tensile strength
- Good conductors of heat and electricity
- Ductile (can be drawn into wires)
- Relatively high densities
- Sonorous (produce a ringing sound when struck)
Exceptions
- Mercury is liquid at room temperature with a melting point of -39°C.
- Sodium and potassium are soft, lightweight metals with low melting points of 97°C and 63°C respectively.
Metals exist as solids at room temperature (except mercury) and form a crystal lattice structure held by strong metallic bonds. Non-metals, in contrast, typically form covalent molecules held by weak intermolecular forces, with exceptions like diamond and graphite (forms of carbon).
Chemical Properties of Metals
- Ionization: Metals have a high tendency to lose electrons and form positive ions, making them electropositive.
- Reducing Ability: Metals act as reducing agents
by donating electrons. For example:
2Na(s) + ½O2(g) → Na2O(s) - Reaction with Acids: Metals more reactive than
hydrogen can displace it from acids. For example:
Zn(s) + 2H+(aq) → Zn2+(aq) + H2(g) - Oxide Formation: Metals react with oxygen to
form basic oxides, which dissolve in water to form alkalis. For
example:
Ca(s) + ½O2(g) → CaO(s)
CaO(s) + H2O(l) → Ca(OH)2(aq) - Reaction with Hydrogen: Very reactive metals
form ionic hydrides by reacting with hydrogen. For example:
2Na(s) + H2(g) → 2NaH(s) - Reaction with Water: Sodium and potassium react vigorously with water, forming metal hydroxides and releasing hydrogen gas. The heat from the reaction may ignite the hydrogen, especially for potassium which burns with a lilac flame. Calcium reacts less violently: Ca(s) + 2H2O(l) → Ca(OH)2(aq) + H2(g) Other metals such as Mg, Al, Zn, Fe, Pb, and Cu react with steam (not cold water) when red hot to produce metal oxides and hydrogen.
Principles of Metal Extraction
Metals are usually found in the Earth's crust as compounds mixed with other substances. To make them useful, they must be extracted. A metal ore is a rock that contains a sufficient concentration of a metal or its compound for extraction to be economically viable.
The extraction method depends on the metal's reactivity:
- Highly reactive metals like aluminium are extracted by electrolysis.
- Less reactive metals like iron can be extracted by reduction with carbon or carbon monoxide.
The Alkali Metals (Group 1 Elements)
General Properties
- All are metals, except hydrogen.
- They react with water to form alkalis.
- Highly electropositive.
- Form univalent positive ions (M+) when ionized.
- Soft, light metals with low melting points due to weak metallic bonds (each atom contributes only one valence electron).
- First ionization energy decreases down the group, so reactivity increases down the group.
- Each element and its ion gives a unique flame color, used for identification.
Sodium
Occurrence
- Lithium occurs in silicate minerals like spodumene [LiAl(SiO3)2] and lepidolite.
- Sodium and potassium compounds have been known since ancient times and make up over 4% of Earth’s crust by weight.
- Sodium chloride (NaCl) is found in seawater and rock salt; it's the main source of sodium.
- Potassium is found in sylvite (KCl) and sylvinite (KCl + NaCl), and carnallite (KCl.MgCl2.6H2O).
- Rubidium and cesium are obtained as by-products in lithium processing.
- Francium is radioactive and rare in nature.
Ores of Sodium
- Albite – NaAlSi3O8
- Borax – Na2B4O7.10H2O
- Glauber’s salt – Na2SO4.10H2O
- Common salt (NaCl) – found in seawater and rock salt
- Sodium nitrate – NaNO3 (Chile saltpetre)
Extraction of Sodium
Sodium was first isolated by Sir Humphrey Davy through electrolysis of fused caustic soda. Two extraction methods include:
- Castner’s Process: Electrolysis of fused caustic soda (NaOH).
- Down’s Process: Electrolysis of fused sodium chloride (NaCl).
Down’s Process
Molten sodium chloride is electrolyzed using a graphite anode and an iron ring cathode. A wire gauge separates the electrodes to avoid sodium and chlorine mixing. A NaCl-KCl-KF mixture is used to lower melting point from 1085 K to ~850-875 K.
Reasons for using a mixture:
- Reduces high temperature requirement.
- Prevents sodium vaporization (as sodium is volatile).
- Prevents corrosion by chlorine gas at high temperatures.
- Ensures sodium is collected as a liquid rather than colloidal form.
Chemical Reactions:
At the cathode:
Na+ + e- → Na
At the anode:
2Cl- → Cl2 + 2e-
Advantages:
- High-purity sodium metal (99.5%).
- Inexpensive starting material (NaCl).
- Chlorine gas is obtained as a valuable by-product.
Physical Properties of Lithium and Sodium
- Light, soft, silvery-white metals (lithium is harder than sodium).
- Sodium can be easily cut with a knife; its shiny surface tarnishes in air.
- Low densities: lithium = 0.634 g/cm³; sodium = 0.97 g/cm³.
- Give flame colors: lithium = crimson red, sodium = golden yellow.
- Have relatively high melting and boiling points.
Chemical Properties of Lithium and Sodium
1. Action of Air
- Stable in dry air, but tarnish in moist air by forming oxides → hydroxides → carbonates.
2. Reaction with Oxygen
- Li burns to form lithium oxide: Li2O
- Na burns to form oxide and peroxide: Na2O and Na2O2
3. Reaction with Water
Both react with cold water, releasing hydrogen gas.
2Li + 2H2O → 2LiOH + H2 2Na + 2H2O → 2NaOH + H2
4. Reaction with Non-metals
- With hydrogen: Forms ionic hydrides.
2Na + H2 → 2NaH
- With chlorine: Forms ionic halides.
2Na + Cl2 → 2NaCl
- With sulphur:
2Na + S → Na2S
- With phosphorus: Forms phosphides.
3Na + P → Na3P
- With nitrogen: Only lithium reacts.
6Li + N2 → 2Li3N
5. Reaction with Ammonia
- Form amides which are reducing agents.
2Na + 2NH3 → 2NaNH2 + H2
6. Reducing Action
They reduce metallic oxides/halides to metals (e.g., beryllium, uranium).
7. Reaction with Acids
Violently react to produce hydrogen gas.
8. Reaction with Mercury
Form sodium amalgams like NaHg, Na2Hg, Na3Hg.
9. Solubility in Liquid Ammonia
Dissolve to give a deep blue, conducting solution due to ammoniated electrons.
Uses of Sodium
- Manufacture of sodium peroxide, sodamide, and sodium cyanide.
- Used in producing tetraethyl lead (anti-knock compound in petrol).
- In alloys and amalgams.
- Used in sodium vapor lamps and illumination engineering.
- As a catalyst for synthetic rubber production.
- As a coolant in nuclear reactors.
- In laboratory (Lassaigne's test).
Compounds of Sodium
Sodium Hydroxide (NaOH)
Physical Properties
- White crystalline solid.
- Deliquescent; melts at ~320°C.
- Dissolves in water exothermically to give strong alkali.
Chemical Properties
- With acids:
2NaOH + H2SO4 → Na2SO4 + 2H2O
- With acidic oxides:
NaOH + SO2 → NaHSO3
- With ammonium salts:
NaOH + NH4Cl → NaCl + H2O + NH3
- With metals (Al, Zn):
2Al + 2NaOH + 6H2O → 2NaAl(OH)4 + 3H2
Zn + 2NaOH + 2H2O → Na2Zn(OH)4 + H2
- To form precipitates:
Zn2+ + 2OH- → Zn(OH)2
Pb2+ + 2OH- → Pb(OH)2
Uses
- Laboratory: Strong alkali, CO2 absorber, analytical reagent.
- Industry: Used in soap, rayon, paper, and refining petroleum.
Sodium Chloride (NaCl)
- White crystalline solid; melts at 801°C and boils at 1420°C.
- Pure NaCl is not deliquescent; impurities like MgCl2 cause deliquescence.
Uses
- Food preservative.
- Raw material for Na, NaOH, Cl2, Na2CO3, etc.
- Used in soap salting, earthenware glazing, water softeners.
Sodium Tetraoxosulphate (IV) – Na2SO4
- Anhydrous form: salt cake.
- Decahydrate: Glauber’s salt (efflorescent).
Uses
- Production of Na2S.
- Purgative.
- Glass, detergent, and wood pulp manufacturing.
Sodium Trioxonitrate (V) – NaNO3
- White solid; melts at 310°C and decomposes on further heating.
Uses
- Nitrogen fertilizer.
- Used in making nitric acid, potassium nitrate, and sodium nitrite.
Sodium Trioxocarbonate (IV) – Na2CO3
- Anhydrous form (soda ash): fine white powder.
- Hydrated form (washing soda): crystalline and efflorescent.
- Dissolves in water to form alkaline solution.
Uses
- Glass manufacturing.
- Water softening.
- Detergent production.
- Used to make NaOH, borax, soap, and paper.
- Standardizing acids and as analytical reagent in labs.
Alkaline Earth Metals (Group II Elements)
Alkaline earth metals do not exist freely in nature. They are typically found as trioxocarbonates(IV) and tetraoxosulphates(VI). Elements in this group include calcium, magnesium, beryllium, strontium, barium, and radium.
Calcium and magnesium compounds form from rock weathering and are found in soil and fresh water as hydrogen trioxocarbonates(IV), tetraoxosulphates(VI), and chlorides — contributing to water hardness. Bones and teeth contain calcium tetraoxophosphate(V). Beryllium is found in small quantities as tetraoxosilicate minerals and is hard to extract. Strontium and radium are less abundant; radium is radioactive.
Physical Properties of Alkaline Earth Metals
- Divalent in nature.
- Possess closely packed metallic structures (except barium).
- Harder than alkali metals due to stronger metallic bonding.
- Softness increases with atomic number.
- Better conductors of heat and electricity than alkali metals.
- Less soluble than alkali metals.
- Have higher melting and boiling points compared to alkali metals.
Chemical Properties
Alkaline earth metals tarnish in air, forming oxides. Beryllium forms a protective oxide layer, unlike the others. When heated in air, they burn to produce oxides and nitrides.
2Mg(s) + O2(g) → 2MgO(s) 3Mg(s) + N2(g) → Mg3N2(s)
Calcium
Occurrence
Calcium is too reactive to occur naturally as a free element. It exists in:
- CaCO3 – limestone, marble, chalk, calcite, coral
- CaSO4 – gypsum and anhydrite
- CaCO3.MgCO3 – dolomite
- CaF2 – fluorspar
Extraction
Metallic calcium is extracted by electrolysis of fused calcium chloride, a by-product of the Solvay process. Calcium fluoride is added to lower the melting point from 850°C to 650°C. Electrolysis is carried out using a graphite-lined crucible (anode) and an iron rod cathode. Calcium deposits on the cathode; chlorine gas is released at the anode.
Chemical Reactions:
At cathode: Ca2+(aq) + 2e- → Ca(s) At anode: 2Cl-(aq) → Cl2(g) + 2e-
Physical Properties of Calcium
- Silvery-white metal
- Malleable and ductile
- Melting point: 851°C
- Good conductor of heat and electricity
- Low tensile strength
- Density: ~1.55 g/cm3
Chemical Properties of Calcium
Reacts readily with air to form calcium oxide. In the presence of moisture and CO2, it forms calcium hydroxide and eventually calcium trioxocarbonate(IV):
2Ca(s) + O2(g) → 2CaO(s) CaO(s) + H2O(l) → Ca(OH)2(s) Ca(OH)2(s) + CO2(g) → CaCO3(s) + H2O(l)
It also reacts with non-metals:
3Ca(s) + N2(g) → Ca3N2(s) Ca(s) + Cl2(g) → CaCl2(s) Ca(s) + H2(g) → CaH2(s)
With water:
Ca(s) + 2H2O(l) → Ca(OH)2(aq) + H2(g)
With ammonia:
3Ca(s) + 2NH3(g) → Ca3N2(s) + 3H2(g)
With dilute acids:
Ca(s) + 2H+(aq) → Ca2+(aq) + H2(g)
Uses of Calcium
- Used in uranium extraction
- Acts as a deoxidizer in steel and copper alloys
- Used in making calcium fluoride and calcium hydride
- Serves as a dehydrating agent for ethanol purification
- Used to remove petroleum impurities
Calcium Oxide (CaO) – Quicklime
Preparation
Produced by heating calcium carbonate above 825°C:
CaCO3(s) → CaO(s) + CO2(g)
Uses
- Generates heat when forming Ca(OH)2:
CaO(s) + H2O(l) → Ca(OH)2(aq) (ΔH = -63.7 kJ/mol)
- Used in limelight for illumination
- Key ingredient in cement
- Used in regenerating NaOH in paper industry
- Forms plaster in ancient flooring
- Used in:
- Refractory bricks
- Manufacture of slaked lime, cement, and calcium carbide
- Neutralizing soil acidity
- Drying agents
- Bleaching agent production
- Iron extraction and glassmaking
Calcium Hydroxide [Ca(OH)2] – Slaked Lime
Properties
- White powder; slightly soluble in water (forms limewater)
- Solubility decreases with temperature
- Decomposes at 480°C:
Ca(OH)2(aq) → CaO(s) + H2O(l)
- Neutralizes acids:
Ca(OH)2(aq) + 2HCl(aq) → CaCl2(s) + 2H2O(l)
- Releases NH3 from ammonium salts:
Ca(OH)2(aq) + 2NH4Cl(s) → CaCl2(s) + 2NH3(g) + 2H2O(l)
- Forms bleaching powder:
Ca(OH)2(s) + Cl2(g) → CaOCl2·H2O(s)
- With cold Cl2:
Ca(OH)2(aq) + 2Cl2(g) → CaCl2(aq) + Ca(OCl)2(aq) + 2H2O(l)
- With hot Cl2:
Ca(OH)2(aq) + 6Cl2(g) → 5CaCl2(aq) + Ca(ClO3)2(aq) + 6H2O(l)
- With CO2:
Ca(OH)2(aq) + CO2(g) → CaCO3(s) + H2O(l)
CaCO3(s) + H2O(l) + CO2(g) → Ca(HCO3)2(aq)
Uses
- Used in slaked lime production
- Softens water (Clark's process)
- Used in glass manufacturing
- Recovers ammonia in the Solvay process
- Purifies coal gas and sugar
- Neutralizes acidic soil
- Lab preparation of ammonia and CO2 testing
- Milk of lime used for whitewashing buildings
Calcium Trioxocarbonate(IV) – CaCO3
Occurrence & Preparation
Occurs naturally as limestone, chalk, coral, and in bones and shells. Prepared by reacting CO2 with calcium hydroxide:
Ca(OH)2(s) + CO2(g) → CaCO3(s) + H2O(l)
Properties
- Reacts with acids to release CO2:
CaCO3(s) + 2HCl(aq) → CaCl2(aq) + H2O(l) + CO2(g)
- Decomposes when heated:
CaCO3(s) → CaO(s) + CO2(g)
- Forms a protective CaSO4 layer with H2SO4, preventing further reaction.
Uses
- Used in making Na2CO3, glass, cement, lime, and steel
- Used in paints, pigments, and fire extinguishers
- Used in construction (marble, limestone)
Calcium Chloride – CaCl2
Properties
- Anhydrous CaCl2 is a white, deliquescent powder:
CaCl2(s) + 5H2O(l) → CaCl2·5H2O(s)
Uses
- Used in desiccators and as a drying agent (not for NH3)
Calcium Tetraoxosulphate(VI) – CaSO4
Properties
- White, non-deliquescent solid
- Solubility increases up to 40°C, then decreases
Uses
- As gypsum, used to make Plaster of Paris (POP)
- Used in manufacturing H2SO4 and (NH4)2SO4
Aluminium
Extraction of Aluminium from Bauxite
Aluminium is highly reactive and cannot be extracted from its ore using carbon reduction because the required temperature would be uneconomical. Instead, it is extracted by electrolysis.
Ore
The primary ore of aluminium is bauxite, an impure form of aluminium oxide. Major impurities include iron oxides, silicon dioxide, and titanium dioxide.
Purification of Aluminium Oxide – Bayer Process
Reaction with Sodium Hydroxide
Crushed bauxite is treated with concentrated sodium hydroxide solution under high temperature (140°C–240°C) and pressure (up to 35 atm). Aluminium oxide dissolves to form sodium tetrahydroxoaluminate while impurities remain as solids and are removed by filtration. The residue is called red mud.
Precipitation of Aluminium Hydroxide
The solution is cooled and seeded with aluminium hydroxide crystals, triggering the precipitation of more aluminium hydroxide.
Formation of Pure Aluminium Oxide
Aluminium hydroxide is heated to about 1100–1200°C to form pure aluminium oxide (Al2O3).
Electrolysis of Aluminium Oxide
The purified aluminium oxide is dissolved in molten cryolite (Na3AlF6) and electrolysed. The molten aluminium collects at the bottom as the cathode product, while oxygen is formed at the carbon anodes.
Electrode Reactions
Cathode:
Al3+ + 3e- → Al(l)
Anode:
2O2- → O2(g) + 4e-
Oxygen reacts with the carbon anodes to form carbon dioxide and carbon monoxide:
C(s) + O2(g) → CO2(g)
2C(s) + O2(g) → 2CO(g)
Properties of Aluminium
1. Reaction with Air
When exposed to air, aluminium forms a thin oxide layer that protects it from further corrosion.
At about 800°C:
4Al(s) + 3O2(g) → 2Al2O3(s)
2Al(s) + N2(g) → 2AlN(s)
2. Reaction with Acids
- Reacts slowly with dilute HCl and more rapidly with concentrated HCl to release hydrogen gas.
- Does not react with dilute H2SO4, but hot concentrated H2SO4 liberates SO2.
- Does not react with HNO3 due to a protective oxide layer formation.
Uses of Aluminium
- Alloyed with elements like silicon, copper, or magnesium to increase strength.
- Low density and good strength when alloyed.
- Excellent conductor of electricity.
- Good surface appearance and corrosion resistance due to oxide layer.
- Used in anodising to enhance corrosion resistance and allow for dyeing.
Common Applications
- Aluminium foil for packaging.
- Al3+ ions (e.g. aluminium sulphate) used as coagulants in water treatment.
- Used in overhead power lines due to lightness and conductivity.
- Used in cookware for being lightweight and a good thermal conductor.
- Powdered aluminium used in mirrors and paints due to its high reflectivity.
- Used to make strong, corrosion-resistant alloys like duralumin and bronze.
- Aluminium powder used in the thermite process for welding metal parts.
Tin (Sn)
Occurrence
Tin occurs naturally as Cassiterite or tinstone, with the chemical formula SnO2. Major deposits are found in Malaysia, Bolivia, and Indonesia. In Nigeria, it is found in smaller quantities in graphite rocks and alluvial deposits, especially in Jos.
Extraction of Tin
- The ore is first crushed and washed using a strong stream of water.
- It is then roasted in air to eliminate impurities like sulphur, arsenic, and antimony as their volatile oxides.
- The resulting tin(IV) oxide (SnO2) is reduced by heating it with coke in a reverberatory furnace.
Chemical Equation:
SnO2(s) + 2C(s) → Sn(l) + 2CO(g)
The molten tin is purified further by heating gently on a sloped surface. As it flows down, impurities are oxidized in air and left behind as scum.
Uses of Tin
- Tin is used to coat steel, protecting it from corrosion via electrolytic deposition or dipping in molten tin.
- It is used in sheet glass production due to its low melting point and resistance to atmospheric corrosion.
- Tin is a component in several alloys such as:
- Bronze (Tin and Copper)
- Solder (Tin and Lead)
- Type Metal (Tin, Antimony, and Lead)
- Tin plating is commonly used in food and drink cans since it is non-toxic.
Iron
Rusting of Iron
Rusting is the corrosion of iron caused by the combined action of oxygen and moisture from the environment. This process is accelerated by pollutants such as carbon dioxide and other gases present in the air. When iron reacts with oxygen and water, it forms a soft, flaky brown substance known as hydrated iron(III) oxide (Fe2O3.xH2O), which breaks off easily.
Reaction: 4Fe(s) + 3O2(g) + 2xH2O(l) → 2Fe2O3.xH2O(s)
Extraction of Iron
Iron is extracted in a blast furnace by reducing its oxide. The iron ore is first roasted in air to produce iron(III) oxide. It is then mixed with coke and limestone and introduced into the furnace. A hot blast of air is blown from the base, initiating the reduction process.
Experiment to Show Air and Moisture Are Required for Rusting
Materials:
- Three test tubes (A, B, and C)
- Iron nails
- Anhydrous calcium chloride
- Boiled tap water
Procedure:
- Place equal numbers of iron nails in each test tube.
- In Tube A, add calcium chloride and seal with a cotton pad and stopper. This removes moisture.
- In Tube B, add boiled water and seal with a stopper and rubber tubing to remove air.
- In Tube C, add tap water and leave it open to air.
Result:
Only the nails in Tube C rusted, showing that both air and water are necessary for rusting.
Prevention of Rusting
- Painting
- Greasing
- Galvanizing
- Electroplating
- Applying enamel
Rusting vs. Burning
- Both involve oxidation, but rusting needs water while burning does not occur easily in the presence of water.
- Burning is rapid, while rusting is a slow process.
- Burning releases large amounts of heat instantly, while rusting releases small amounts over time.
Types of Iron
- Pig Iron
- Cast Iron
- Wrought Iron
Physical Properties of Iron
- Silvery in color with high tensile strength
- Malleable and ductile
- Easily magnetized
- Melting point: 1530°C
- Density: 7.9 g/cm3
- Good conductor of heat and electricity
Chemical Properties of Iron
- Reaction with air: Forms rust
- Reaction with steam: 3Fe + 4H2O → Fe3O4 + 4H2
- Reaction with non-metals:
- 2Fe + 3Cl2 → 2FeCl3
- Fe + S → FeS
- 2Fe + P4 → Fe2P
- 2Fe + 2C → 2Fe3C
- Reaction with acids: Fe + 2HCl → FeCl2 + H2
Test for Iron(II) Ions
- Add NaOH solution: dirty-green precipitate forms, insoluble in excess.
- Add NH3: dirty-green precipitate forms, insoluble in excess.
- Add potassium hexacyanoferrate(III): forms dark blue precipitate.
Test for Iron(III) Ions
- Add NaOH solution: reddish-brown precipitate forms, insoluble in excess.
- Add NH3: reddish-brown precipitate forms, insoluble in excess.
- Add potassium hexacyanoferrate(II): forms a blue precipitate.
The Transition Metals
Transition elements are found between Group II and Group III of the periodic table and share similar chemical behavior. They are also known as the d-block elements because electrons are progressively added to their d-subshells.
Examples include: Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn.
They are all metals and exhibit typical metallic properties such as high tensile strength and high melting points. Unlike Group I and II metals, transition metals are less reactive and have distinctive characteristics.
General Properties of First Row Transition Elements
- They exhibit variable oxidation states.
- They form coloured compounds.
- They can form complex ions.
- They are paramagnetic (attracted to magnetic fields).
- They often act as catalysts in chemical reactions.