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Limestone - a very useful material Limestone, is a sedimentary rock formed by the mineral and 'shelly' remains of marine organisms, including coral, in warm shallow fertile seas. It is chemically mainly calcium carbonate and is a useful material that is quarried and used directly as a building material. It reacts with acids - 'fizzing' due to carbon dioxide formation - test with 'limewater' - milky white precipitate. o Marble is also made of calcium carbonate and is a metamorphic rock formed by the action of heat and pressure on limestone in the Earth's crust. It is a much harder rock than limestone and is used to make highly polished and finely carved stone sculptures, statues etc. Chemically, limestone mainly consists of calcium carbonate, CaCO3, and is a valuable natural mineral resource, quarried in large quantities in many countries (see environmental impact at the end of the metal extraction web page). Other uses of limestone rock are outlined below and it is an important raw material in the manufacture of cement, concrete, glass and iron. Powdered limestone can be used to neutralise acidity in lakes and soils. (neutralisation chemistry). Like lime, it is a safe agri-chemical to use on the land and does produce the controversial side effects of artificial fertilisers, herbicides and pesticides etc. What happens when limestone is strongly heated? When limestone is heated in a kiln at over 900 C, it breaks down into quicklime (calcium oxide) and carbon dioxide. Both are useful products. This type of reaction is endothermic (heat absorbing) and an example of thermal decomposition (and other carbonates behave in a similar way).

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calcium carbonate (limestone) ==> calcium oxide (quicklime) + carbon dioxide CaO(s) + CO2(g)

CaCO3(s) acidity.

Quiclime (calcium oxide) is used in steel making and spread on land to reduce soil

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This is a reversible endothermic reaction. To ensure the change is to favour the right hand side, a high temperature of over 900 C is needed as well as the continual removal of the carbon dioxide. The high temperature needed is produced by mixing the limestone with coal/coke (a fuel of mainly carbon) and blowing hot air into the ignited mixture in a rotating kiln for a continuous production line (raw materials in at one end, lime out the other!) .... C(s) + O2(g) ==> CO2(g) is very exothermic - heat releasing! These also show a similar thermal decomposition to calcium carbonate e.g. copper(II) carbonate(green) ==> copper(II) oxide(black) + carbon dioxide CuCO3(s) ==> CuO(s) + CO2(g) zinc carbonate(white) ==> zinc oxide(yellow hot, white cold) + carbon dioxide ZnCO3(s) ==> ZnO(s) + CO2(g) magnesium carbonate(white) ==> magnesium oxide(white) + carbon dioxide MgCO3(s) ==> MgO(s) + CO2(g) Zinc carbonate occurs as the mineral ores calamine/Smithsonite and the resulting zinc oxide can be used to extract zinc metal and zinc oxide itself is used as a whitening agent' in cosmetics and in 'calamine lotion' a mild antiseptic and antipruritic (anti-itching agent) for treating skin irritations.

Note on heating other carbonates you get a similar thermal decomposition.

FeCO3 and MnCO3 behave in a similar way iron(II) carbonate(s) ==> iron(II) oxide(s, black) + carbon dioxide

FeCO3(s) ==> FeO(s) + CO2(g) manganese(II) carbonate(s, white) ==> manganese(II) oxide(s, white) + carbon dioxide MnCO3(s) ==> MnO(s) + CO2(g)

Sodium hydrogen carbonate is used in baking powder because on heating it thermally decomposes releasing carbon dioxide gas that gives the 'rising' action in baking. sodium hydrogencarbonate ==> sodium carbonate + water + carbon dioxide 2NaHCO3(s) ==> Na2CO3(s) + H2O(l/g) + CO2(g) This is just one of many chemical process that occur when food is cooked.

Quicklime reacts very exothermically with water to produce slaked lime (solid calcium

hydroxide). calcium oxide (quicklime) + water ==> calcium hydroxide (slaked lime) this is a very exothermic reaction, the quicklime 'puffs' up and steam is produced! CaO(s) + H2O(l) ==> Ca(OH)2(s) with excess water followed by filtration you get calcium hydroxide solution or limewater.

Lime (calcium oxide) and slaked lime (calcium hydroxide) are both used to reduce the acidity of soil on land, they are both faster and stronger acting than limestone powder. o They are also used to reduce acidity in lakes and rivers due to acid rain.

They are also used to neutralise potentially harmful industrial acid waste including sulphur dioxide in the flue gases of power stations. In the test for carbon dioxide, calcium hydroxide solution (limewater) forms a white milky precipitate of calcium carbonate (back to where you started!). o calcium hydroxide + carbon dioxide ==> calcium carbonate + water o Ca(OH)2(aq) + CO2(g) ==> CaCO3(s) + H2O(l) Formulae of magnesium and calcium compounds (M = metal = Mg or Ca, same group 2, same formula!) 2+ o IONS: The metal ion in aqueous solution or solid compounds is M , which combines with other ions 22-, such as: oxide O , hydroxide OH , carbonate CO3 , hydrogencarbonate HCO3 chloride Cl , 2sulphate SO4 , nitrate NO3 to form the calcium or magnesium compounds. o COMPOUND FORMULAE: oxide MO, hydroxide M(OH)2, carbonate MCO3, hydrogencarbonate M(HCO3)2, chloride MCl2, sulphate MSO4, nitrate M(NO3)2 The oxides and hydroxides readily react with acids to form salts o o (more details on the pH, Acids, Bases, Salts pages) general word equation: oxide or hydroxide + acid ==> salt + water examples ... calcium oxide + hydrochloric acid ==> calcium chloride + water magnesium hydroxide + nitric acid ==> magnesium nitrate + water calcium hydroxide + sulphuric acid ==> calcium sulphate + water since hydrochloric acid gives a chloride salt, nitric acid gives a nitrate salt, sulphuric acid a sulphate salt ... the symbol equations are ... where M = Mg or Ca (or any other Group 2 metal) MO(s) + 2HCl(aq) ==> MCl2(aq) + H2O(l) MO(s) + 2HNO3(aq) ==> M(NO3)2(aq) + H2O(l) MO(s) + H2SO4(aq) ==> MSO4(aq/s*) + H2O(l) if M(OH)2 involved, there is a 2H2O at the end NOT a single H2O to balance the symbol equation M(OH)2(s) + 2HCl(aq) ==> MCl2(aq) + 2H2O(l) M(OH)2(s) + 2HNO3(aq) ==> M(NO3)2(aq) + 2H2O(l) M(OH)2(s) + H2SO4(aq) ==> MSO4(aq/s*) + 2H2O(l) * the sulphates of e.g. calcium and barium are not very soluble and this slows the reaction down! Solubility of calcium compounds (and the chemically similar magnesium): o Magnesium and calcium oxides or hydroxides are slightly soluble in water forming alkaline solutions. They readily react and dissolve in most acids (see above).

Magnesium and calcium carbonate are insoluble in water but readily dissolve in most dilute acids like hydrochloric, nitric and sulphuric. o Equation examples for calcium carbonate (similar for magnesium carbonate) ... o calcium carbonate + hydrochloric acid ==> calcium chloride + water + carbon dioxide CaCO3(s) + 2HCl(aq) ==> CaCl2(aq) + H2O(l) + CO2(g) o calcium carbonate + nitric acid ==> calcium nitrate + water + carbon dioxide CaCO3(s) + 2HNO3(aq) ==> Ca(NO3)2(aq) + H2O(l) + CO2(g) o calcium carbonate + sulphuric acid ==> calcium sulphate + water + carbon dioxide CaCO3(s) + H2SO4(aq) ==> CaSO4(aq,s) + H2O(l) + CO2(g) Calcium carbonate reacts slowly in dilute sulphuric acid because calcium sulphate is not very soluble and coats the limestone inhibiting the reaction. Magnesium and calcium hydrogencarbonate are soluble in water and cause 'hardness' i.e. scum with 'traditional' non-detergent soaps. Formulae are Mg(HCO3)2 and Ca(HCO3)2 Cement is produced by roasting a mixture of powdered limestone with powdered clay* in a rotary kiln. When cement is mixed with water, sand and crushed rock, a slow chemical reaction produces a hard, stonelike building material called concrete. o * Clay is also used directly to make pottery and other ceramics Glass is made by heating together a mixture of limestone (CaCO3), sand (mainly silica = silicon dioxide = SiO2) and 'soda' (sodium carbonate, Na2CO3). Limestone is used to remove acidic oxide impurities in the extraction of iron and in making steel. Calcium oxide and calcium hydroxide also react with acids to form salts. You will find details of this kind of reaction on the Acids and Bases page o or in the calcium/magnesium salt formation section above. Limestone and hard/soft water are covered on the Extra Aqueous Chemistry page.

Other thermal decompositions (not needed by some syllabuses)

See also s-block Group I/II detailed notes for advanced level chemistry students Decomposition of carbonates: see above. Decomposition of metal hydroxides: o The Group 1 Alkali Metal hydroxides do not readily decompose on heating even 'up to red heat'. o Except for lithium hydroxide which forms lithium oxide and water. 2LiOH(s) ==> Li2O(s) + H2O(l)

These hydroxides are white solids and soluble in water to give an alkaline solution.

On heating, the Group II, Lead, Aluminium and Transition Metal hydroxides decompose to form the

metal oxide and water vapour. o The original hydroxides are usually relatively insoluble solids, white in colour, except copper(II) hydroxide is blue and iron(III) hydroxide is brown. M(OH)2(s) ==> MO(s) + H2O(l) M = Mg, Ca, Zn giving white oxide MO (ZnO yellow when hot), M = Cu gives black copper(II) oxide CuO, M = Pb gives yellow lead(II) oxide PbO e.g. if M = Zn: zinc hydroxide ==> zinc oxide + water o o Zn(OH)2(s) ==> ZnO(s) + H2O(l) or Ca(OH)2(s) ==> CaO(s) + H2O(l) to give calcium oxide (quicklime)

and 2M(OH)3(s) ==> M2O3(s) + 3H2O(l) where M = Al to give white aluminium oxide, and M = Fe to give reddish-brown iron(III) oxide. e.g. 2Al(OH)3(s) ==> Al2O3(s) + 3H2O(l)

Decomposition of nitrate salts: The Group 1 Alkali Metal nitrates (NO3) decompose to form the nitrite (NO2) salt and oxygen gas. 2MNO3(s) ==> 2MNO2(s) + O2(g) where M = Na or K so when M = Na/K: sodium/potassium nitrate ==> sodium/potassium nitrite + oxygen Nitrates are colourless crystals and nitrites are white solids and are all soluble in water giving neutral solutions.

Many metal nitrates decompose to form the metal oxide, nasty brown nitrogen dioxide gas (NO2) and oxygen gas (O2) when strongly heated. These nitrates are all water soluble neutral salts, all colourless crystals except Cu is blue and Fe is pale brown-dark orange. 2M(NO3)2(s) ==> 2MO(s) + 4NO2(g) + O2(g)

where M = Mg, Ca, Zn giving the white oxide MO (ZnO yellow when hot), when M = Cu, it gives the black copper(II) oxide CuO if M = Pb it gives the yellow lead(II) oxide PbO. e.g. lead(II) nitrate ==> lead(II) oxide + nitrogen dioxide + oxygen 2Pg(NO3)2(s) ==> 2PbO(s) + 4NO2(g) + O2(g)

4M(NO3)3(s) ==> 2M2O3(s) + 12NO2(g) + 3O2(g) If M = Al, it gives white aluminium oxide, if M = Fe it gives give reddish-brown iron(III) oxide. e.g. 4Al(NO3)3(s) ==> 2Al2O3(s) + 12NO2(g) + 3O2(g)


gas preparation and collection page for methods.