Official JEE Chemistry Revision Material: JEE Chemistry S Block Elements Notes Set 04
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Group 2: General Trends
The alkaline earth metals (Be, Mg, Ca, Sr, Ba, Ra) have two outer electrons, ns2. They are harder, denser and have higher melting points than group 1 metals because two electrons take part in metallic bonding. They form M2+ ions and mostly ionic compounds, with the exception of beryllium.
| Property | Trend (Be to Ba) | Reason |
|---|---|---|
| Ionisation energy (first) | Decreases | Larger size |
| Hydration energy of M2+ | Decreases | Larger ion, lower charge density |
| Basic strength of oxides and hydroxides | Increases | Bonds to oxygen become more ionic |
| Solubility of hydroxides | Increases | Lattice energy falls more slowly than hydration energy |
| Solubility of sulphates and carbonates | Decreases | Hydration energy falls faster than lattice energy |
| Thermal stability of carbonates and sulphates | Increases | Larger cations polarise the anion less |
| Flame colour | Ca brick red, Sr crimson, Ba apple green; Be and Mg none | Be and Mg need too much excitation energy |
Anomalous Behaviour of Beryllium and Diagonal Relationship with Aluminium
1. Be is tiny with high charge density, so its compounds are largely covalent; BeCl2 is a chain polymer in the solid, a dimer and a monomer in vapour.
2. BeO and Be(OH)2 are amphoteric, like Al2O3 and Al(OH)3. The other group 2 oxides are basic.
3. Be does not give a flame colour, does not form a peroxide, and forms complexes such as BeF4(2-) because its valence shell has no d-orbitals but the small ion is a good electron-pair acceptor.
4. Be2C gives methane with water, as does Al4C3; CaC2 gives ethyne.
5. BeCl2 is easily hydrolysed and fumes in moist air; both Be and Al are rendered passive by concentrated nitric acid.
Reactions of the Alkaline Earth Metals
1. Air: burn to give the oxide MO and nitride M3N2; Ba (and Sr) can form peroxides on heating in oxygen.
2. Water: Be does not react, Mg reacts with steam, and Ca, Sr, Ba react with cold water to give the hydroxide and hydrogen.
3. Hydrides: Ca, Sr, Ba hydrides are ionic; BeH2 and MgH2 are covalent. BeH2 is made from BeCl2 and LiAlH4.
4. Carbides: CaC2 on hydrolysis gives acetylene; Be2C gives methane; Mg2C3 gives propyne.
5. Solutions in liquid ammonia: group 2 metals also dissolve to give blue-black solutions with ammoniated electrons.
Important Calcium and Magnesium Compounds
| Compound | Preparation or key fact | Uses |
|---|---|---|
| Quicklime CaO | Heating limestone at about 1070 to 1270 K; basic, reacts with water to form slaked lime | Steel making, cement, drying agent, causticisation |
| Slaked lime Ca(OH)2 | CaO + H2O; lime water turns milky with CO2 and clear again with excess CO2 (Ca(HCO3)2 forms) | Mortar, softening of water, bleaching powder |
| Plaster of Paris CaSO4.1/2H2O | Heating gypsum CaSO4.2H2O at about 393 K; at about 473 K the water is all lost to give dead burnt plaster. It sets back to gypsum on mixing with water. | Plasters, casts, statues, moulds |
| Portland cement | Clinker from limestone and clay heated at about 1800 K, ground with gypsum to slow the setting. Main constituents are Ca3SiO5, Ca2SiO4 and Ca3Al2O6. | Construction |
| Magnesium hydroxide | Milk of magnesia, a mild antacid | Medicine |
| Epsom salt MgSO4.7H2O | Hydrated sulphate | Purgative |
| Dolomite CaCO3.MgCO3, carnallite KCl.MgCl2.6H2O | Minerals; electrolysis of fused carnallite (after dehydration) gives magnesium | Refractories, source of Mg |
Hard Water
Hardness is due to soluble salts of Ca and Mg that form scum with soap. Temporary hardness is caused by bicarbonates and is removed by boiling or by Clark's method (adding lime). Permanent hardness is caused by chlorides and sulphates and is removed by washing soda, by Calgon (sodium hexametaphosphate), by ion exchange (zeolite or resins) or by EDTA complexation. EDTA titration is used to estimate Ca2+ and Mg2+.
Biological Role
Mg2+ is at the centre of chlorophyll and activates ATP-dependent enzymes. Ca2+ builds bones and teeth, is needed for blood clotting, muscle contraction and nerve impulses. Fluoride in drinking water (about 1 ppm) converts hydroxyapatite in tooth enamel into harder fluoroapatite.
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