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Calcium Carbonate / Limestone

• 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.

• It is a valuable natural mineral resource and is quarried in large quantities


in many countries (see environmental impact).

• Other uses of limestone rock are outlined below and it is an important


raw material in the manufacture of cement and glass and iron.

• Powdered limestone can be used to neutralise acidity in lakes and


soils. (Neutralisation chemistry).

• When limestone is heated in a kiln at over 900oC, it breaks down


into quicklime (calcium oxide) and carbon dioxide. Both are useful
products. This type of reaction is endothermic and an example of
thermal decomposition (and other carbonates behave in a similar
way).

o Calcium carbonate (limestone) ==> calcium oxide (quicklime) +


carbon dioxide

o CaCO3(s) CaO(s) + CO2(g)

o This is a reversible endothermic reaction. To ensure the change


is to favour the right hand side, a high temperature of over 900oC is
needed as well as the continual removal of the carbon dioxide.

o 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!) ....

o C(s) + O2(g) ==> CO2(g) is very exothermic!

• Note on other carbonates These also show a similar thermal


decomposition to CaCO3 above ...

o copper(II) carbonate(green) ==> copper(II) oxide(black) + carbon


dioxide

o CuCO3(s) ==> CuO(s) + CO2(g)

o zinc carbonate(white) ==> zinc oxide(yellow hot, white cold) + carbon


dioxide

o ZnCO3(s) ==> ZnO(s) + CO2(g)

o FeCO3 and MnCO3 behave in a similar way

• Quicklime reacts very exothermically with water to produce slaked


lime (calcium hydroxide).
o 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)

• 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. 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 = Mg or Ca,


same group, same formula!)

o IONS: ion in aqueous solution is M2+(aq), other ions in their


compounds: oxide O2-, hydroxide OH-, carbonate CO32-,
hydrogencarbonate HCO3-, chloride Cl-, sulphate SO42-, nitrate NO3-

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.

o 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
o 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 2H20 NOT a single H2O to


balance the equation

 * the sulphates of eg calcium and barium are not very


soluble, 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).

o Magnesium and calcium carbonate are insoluble in water but


readily dissolve in most dilute acids like hydrochloric, nitric and
sulphuric. Calcium carbonate reacts slowly in dilute sulphuric acid
because calcium sulphate is not very soluble and coats the
limestone

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)

• Magnesium and calcium hydrogencarbonate are soluble in water


and cause 'hardness' ie 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,
stone-like building material called concrete.

o * Clay is used directly to make pottery and other ceramics

• Glass is made by heating 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.

Other thermal decompositions


• Decomposition of carbonates: dealt with above.

• Decomposition of metal hydroxides:

o The Group 1 Alkali Metal hydroxides do not readily decompose on heating


'upto red heat'.

 Except for lithium hydroxide which forms lithium oxide and


water.

 2LiOH(s) ==> Li2O(s) + H2O(l)

 These hydroxides are white solids soluble in water to give an


alkaline solution.

o On heating the Group II, Lead, Aluminium and Transition Metal


hydroxides decompose to form the metal oxide and water vapour.

 The original hydroxides are usually relatively insoluble solids,


white in colour, except Cu is blue and Fe is brown.

o M(OH)2(s) ==> MO(s) + H2O(l)

 M = Mg, Ca, Zn giving white oxide MO (ZnO yellow when hot),

 M = Cu gives black CuO, M = Pb gives yellow PbO

o and 2M(OH)3(s) ==> M2O3(s) + 3H2O(l)

 where M = Al to give white oxide and M = Fe to give reddish-


brown oxide
• Decomposition of nitrate salts:

o The Group 1 Alkali Metal nitrates (NO3) decompose to form the nitrite
(NO2) salt and oxygen gas.

 They are white soluble solids giving neutral solutions.

 2MNO3(s) ==> 2MNO2(s) + O2(g) where M = Na or K

o The Group II, Lead, Aluminium and Transition Metal nitrates decompose
to form the metal oxide, nasty brown nitrogen dioxide gas and oxygen
gas when strongly heated.

 These are all water soluble neutral salts, all colourless crystals
except Cu is blue and Fe is pale brown.

 2M(NO3)2(s) ==> 2MO(s) + 4NO2(g) + O2(g)

 where M = Mg, Ca, Zn giving white oxide MO (ZnO yellow


when hot),

 M = Cu gives black CuO, M = Pb gives yellow PbO

 when M = Cu gives black CuO, M = Pb gives yellow PbO

 4M(NO3)3(s) ==> 2M2O3(s) + 12NO2(g) + 3O2(g)

 M = Al giving white oxide, M = Fe to give reddish-brown


oxide