Iron and its compounds

Iron is a silvery malleable and ductile metallic transition element. Its atomic number is 26. It has r.a.m. being equal to 55.847. Its relative density is 7.87. Its melting point is 1535°C and boiling point is 2750°C. The main sources are the ores haematite (Fe₂O₃), magnetite (Fe₃O₄), limonite (FeO (OH)_nH₂O), ilmenite (FeTiO₃), siderite (FeCO₃) and pyrite (FeS₂). The metal is smelted in a blast furnace to give impure pig iron, which is further processed to give cast iron, wrought iron and various types of steel. The pure element has three crystal forms: alpha-iron,stable below 906°C with a body-centered-cubic structure; gamma-iron, stable between 906°C and 1403°C with a nonmagnetic face-centered-cubic structure; and delta-iron, which is the body-centered-cubic form above 1403°C. Alpha-iron is ferromagnetic up to its Curie point (768°C). The element has nine isotopes (mass numbers 52-60) and is the fourth most abundant in the Earth's crust. It is required as a trace elementby living organisms. Iron is quite reactive, being oxidized by moist air, displacing hydrogen from dilute acids, and combining with nonmetallic elements. It forms ionic salts and numerous complexes with the metal in the +2 or +3 oxidation states. Iron (VI) also exists in the ferrate ion FeO₄^2-and the element also forms complexes in which its oxidation number is zero (e.g. Fe (CO)₅).

Iron (II) chloride is a green-yellow deliquescent compound, FeCl₂. Its shape is hexagonal. Its relative density is 3.16. It has melting point being equal to 670°C. It also exists in hydrated forms: FeCl₂.2H₂O (green monoclinic; relative density is 2.36) and FeCl₂.4H₂O (blue-green monoclinic deliquescent; relative density is 1.93). Anhydrous iron (II) chloride can be made by passing a stream of dry hydrogen chloride over the heated metal. The hydrated forms can be made using dilute hydrochloric acid or by recrystallizing with water. It is converted into iron (III) chloride by the action of chlorine.

Iron (III) chloride is a black-brown solid, FeCl₃. Its shape is hexagonal. Its relative density is equal to 2.9 and melting point is equal to 306°C. It decomposes at 315°C. It also exists as the hexahydrate FeCl₃.6H₂O, a brown-yellow deliquescent crystalline substance (melting point is 37°C; boiling point is 280-285°C). Iron (III) chloride is prepared by passing dry chlorine over iron wire or steel wool. The reaction proceeds with incandescence when started and iron (III) chloride sublimes as almost black iridescent scales. The compound is rapidly hydrolysed in moist air. In solution it is partly hydrolysed. Hydrolysis can be suppressed by the addition of hydrochloric acid. The compound dissolves in many organic solvents, forming solutions of low electrical conductivity. In ethanol, ethoxyethane and pyridine the molecular weight corresponds to FeCl₃ but is higher in other solvents corresponding to Fe₂Cl₆. The vapour is also dimerized. In many ways the compound resembles aluminium chloride, which it may replace in Friedel-Crafts reactions.

Iron (II) oxide is a black solid, FeO. Its shape is cubic. It has relative density being equal to 5.7. its melting point is 1420°C. It can be obtained by heating iron (II) oxalate. The carbon monoxide formed produces a reducing atmosphere thus preventing oxidation to iron (III) oxide. The compound has the sodium chloride structure, indicating its ionic nature, but the crystal lattice is deficient in iron (II) ions and it is nonstoichiometric. Iron (II) oxide dissolves readily in dilute acids.

Iron (III) oxide is a red-brown to black insoluble solid, Fe₂O₃. Its shape is trigonal. Its relative density is equal to 5.24 and melting point is 1565°C. There is also a hydrated form, Fe₂O₃.xH₂O, which is a red-brown powder. Its relative density is 2.44-3.60. Iron (III) oxide occurs naturally as haematite and can be prepared by heating iron (III) hydroxide or iron (II) sulphate. It is readily reduced on heating in a stream of carbon monoxide or hydrogen.

Iron (II) sulphate is an off-white solid, FeSO₄.H₂O. Its shape is monoclinic. Its relative density is 2.970. There is also a heptahydrate, FeSO₄.7H₂O. It is blue-green monoclinic with relative density of 1.898 and melting point of 64°C. The heptahydrate is the best known iron (II) salt and is sometimes called green vitriol or copperas. It is obtained by the action of dilute sulphuric acid on iron in a reducing atmosphere. The anhydrous compound is very hygroscopic. It decomposes at red heat to give iron (III) oxide, sulphur trioxide and sulphur dioxide. A solution of iron (II) sulphate is gradually oxidized on exposure to air, a basic iron (III) sulphate being deposited.

Iron (III) sulphate is a yellow hygroscopic compound, Fe₂(SO₄)₃. Its shape is rhombic. Its relative density is 3.097. It decomposes above 480°C. It is obtained by heating an aqueous acidified solution of iron (II) sulphate with hydrogen peroxide:

2FeSO₄ + H₂SO₄ + H₂O₂ ® Fe₂(SO₄)₃ + 2H₂O.

On crystallizing, the hydrate Fe₂(SO₄)₃.9H₂O is formed. The acid sulphate Fe₂(SO₄)₃.H₂SO₄.8H₂O is deposited from solutions containing a sufficient excess of sulphuric acid.

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Exercise 8.	\|	Nickel and its compounds

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