Sie sind auf Seite 1von 7

A is a white compound of lead; on heating it gives yellow B and a colourles gas that turns limewater milky.

If B is heated in air for several hours at 470oC it is converted into a scarlet powder C. C contains 90.66% lead and 9.34% oxygen by mass. C on heating with dilute aqueous nitric acid gives a colourless solution D and a brown solid E. If sodium hydroxide solution is added to solution D, a white gelatinous precipitate is formed, which with excess sodium hydroxide solution gives a colourless solution G. Compound E reacts with concentrated hydrochloric acid to give a white solid I and a green gas J. I is soluble in hot water but insoluble in cold, and forms soluble complex ions such as K with excess chloride ions. With potassium iodide solution J gives a brown solution of L, which on shaking with hexane gives a deep purple organic layer. With potassium iodide solution D gives a bright yellow solid M; this is insoluble in cold water, but in hot water gives a colourless solution. Identify all the substances A - M, and write equations for all the reactions involved. ===================================================================== The evolution of carbon dioxide on heating A suggests that it is a carbonate, lead(II) carbonate; the residue B is therefore an oxide, lead(II) oxide: A B: PbCO3 PbO + CO2

On prolonged heating at 470oC lead(II) oxide (which is also called litharge) partially oxidises to the mixed oxide Pb3O4 which contains both lead(II) and lead(IV) ions. B C: 6PbO + O2 2 Pb3O4

Pb3O4 is scarlet and is also known as red lead and as minium. It behaves as PbO2.2PbO. With nitric acid the basic lead(II) oxide portion reacts to give a solution of lead(II) nitrate, D, and a residue of lead(IV) oxide, E: C D + E: Pb3O4 + 4HNO3 2Pb(NO3)2 + PbO2 + 2H2O.

With lead(II) nitrate solution sodium hydroxide gives an initial precipitate of lead(II) hydroxide F; this substance is amphoteric and reacts with more sodium hydroxide to give a solution of sodium plumbate(II), G, which is colourless: D F: Pb(NO3)2 + 2NaOH Pb(OH)2 + 2NaNO3

or, ionically, Pb2+ + 2OH- Pb(OH)2.

F G:

Pb(OH)2 + 2NaOH Na2Pb(OH)4

Or, ionically, Pb(OH)2 + 2OH - [Pb(OH)4]2-. Lead(IV) oxide is a strong oxidising agent and oxidises concentrated HCl to chlorine, J, and lead(II) chloride I. Lead(II) chloride complexes with chloride ions to give various species such as PbCl3- and PbCl42-, which are yellow and water-soluble: E I + J: PbO2 + 4HCl PbCl2 + 2H2O + Cl2. J K: PbCl2 + Cl- PbCl3- .

Chlorine oxidises potassium iodide solution to iodine, L, which in the presence of excess iodide ions gives a brown solution of the tri-iodide ion: J L: Cl2 + 2I- I2 + 2ClI2 + I- I3- .

Lead(II) nitrate solution gives a precipitate of lead(II) iodide M with potassium iodide solution. Lead(II) iodide is bright yellow when solid, but gives a colourless solution in hot water, from which shimmering yellow plates crystallise on cooling. The colour arises from interactions in the crystal lattice and not from the ions themselves, both of which are colourless: D M: Pb2+ + 2I- PbI2 .

Copper reacts with 50% nitric acid to give a blue solution A and a brown gas B. If the solution A is diluted and sodium hydroxide solution added cautiously, a gelatinous blue precipitate C is obtained, which if warmed forms a black solid G. Addition of concentrated ammonia solution to C gives a deep blue solution that contains the ion D. Addition of concentrated hydrochloric acid to C gives a green solution of the ion E, which on dilution with water gives a solution of the ion F. If the brown gas B is passed into water a mixture of acids H and I is formed in a disproportionation reaction. Identify A - I, giving equations for and explaining each reaction as far as possible. The reaction of copper with nitric acid is complicated and depends on the concentration of the acid and its temperature. With 50% acid the initial reaction, to give copper(II) nitrate A and nitrogen dioxide B is: Cu + 4HNO3 Cu(NO3)2 + 2NO2 + 2H2O.

If sodium hydroxide is added to a solution of copper(II) nitrate, a pale blue precipitate is given, usually represented as copper(II) hydroxide. Cu(NO3)2 + 2NaOH Cu(OH)2 + 2NaNO3 The reaction is actually with the hydrated copper ions themselves, which are deprotonated: [Cu(H2O)6]2+ + 2OH- Cu(OH)2 + 6H2O. However, if as here the sodium hydroxide is added to the solution of the copper(II) salt, the precipitate is not the hydroxide, but the basic nitrate Cu(OH)2.Cu(NO3)2 (or sulphate, or chloride, depending on the copper(II) salt employed). To get the true hydroxide, the copper(II) salt has to be added to sodium hydroxide solution. The business of hydroxide precipitates is convoluted to say the least - take a look at my article on the subject. For the purposes of this answer, C is copper(II) hydroxide. On heating (even in aqueous suspension) copper(II) hydroxide loses water to give G, copper(II) oxide, as a black precipitate: C G: Cu(OH)2 CuO + H2O.

Copper(II) nitrate solution reacts with aqueous ammonia in a ligand replacement reaction to give the tetrammine complex, which is deep blue and is D: A D: [Cu(H2O)6]2+ + 4NH3 [Cu(NH3)4(H2O)2]2+ + 4H2O

If a large excess of chloride ions is added to D, ligand replacement occurs to give the tetrahedral CuCl42- ion, E, which is bright green: D E: [Cu(NH3)4(H2O)2]2+ + 4H + + 4Cl- [CuCl4]2- + 2H2O + 4NH4 +

Dilution of this solution E results in replacement of the chloride ligands by water, and solution F contains hexaquacopper(II), pale blue: E F: [CuCl4]2- + 6H2O [Cu(H2O)6]2+ + 4Cl - .

Nitrogen dioxide reacts with water to give a mixture of nitrous and nitric acids; the nitrogen goes from oxidation state (+4) in NO2 to (+3) in nitrite and (+5) in nitrate. Nitrogen is simultaneously oxidised and reduced so the reaction is disproportionation: B H + I: 2NO2 + H2O HNO2 + HNO3


A white powder A on heating turns yellow and evolves a gas C that turns limewater milky, as well as water vapour. The yellow residue B turns white on cooling, but will turn yellow again when heated. B reacts with dilute sulphuric acid to give a colourless solution D. If dilute sodium hydroxide solution is added to D, a white precipitate E is produced which with excess alkali gives a colourless solution F. With dilute ammonia solution D gives a white precipitate G; adding excess ammonia causes the mixture to become clear, giving solution H. Identify all the substances A H, and account as thoroughly as you can for the observations. The evolution of carbon dioxide C from A suggests that A is a carbonate; the yellow residue that turns white on cooling is zinc oxide, C. This colour change is unique, and depends on zinc ions moving a little in the crystal lattice as it is heated, returning to their original positions on cooling. You might therefore say that A is ZnCO3. This substance does not exist; zinc carbonate is a basic salt, ZnCO3.2Zn(OH)2, that is has zinc hydroxide incorporated in the lattice. Zinc hydroxide loses water on heating and also forms zinc oxide. Its presence accounts for the water vapour that was observed: A B + C: ZnCO3.2Zn(OH)2 3ZnO + 2H2O + CO2.

Zinc oxide gives a solution of zinc sulphate, D, with dilute sulphuric acid, but all the subsequent reactions are of the zinc ion [Zn(H2O)6]2+, so I shall use ionic equations and leave the spectator sulphate ion out: B D: ZnCO3.2Zn(OH)2 + 6H+ + 15 H2O 3 [Zn(H2O)6]2+ + CO2. This is perhaps a bit daunting, and since basic salts are not in the Edexcel syllabus a satisfactory equation is B D: ZnCO3 + 2H+ + 6H2O [Zn(H2O)6]2+ + H2O + CO2.

Solution D with sodium hydroxide gives a precipitate of zinc hydroxide, E, which being amphoteric reacts further with hydroxide ions to give the zincate ion F, which is soluble and colourless: D E: [Zn(H2O)6]2+ + 2OH- Zn(OH)2 + 6H2O E F: Zn(OH)2 + 2OH- [Zn(OH)4]2-

Ammonia also precipitates zinc hydroxide G from aqueous solutions of zinc ions. In excess ammonia this reacts further to give the colourless and soluble tetramminezinc(II) ion: Zn(OH)2 + 4NH3 [Zn(NH3)4]2+ + 2OH-

Basic zinc carbonate occurs naturally as the mineral calamine, which has long been used as part of a lotion for skin disorders, and which is used to promote healing. Zinc oxide, as an ointment or in plasters or dressings, is used for the same purpose, and although poisonous in large quantities zinc is a necessary trace element for health. A is a metal that reacts moderately quickly with dilute sulphuric acid to give a pale green solution B and a gas C. If solution B is allowed to crystallise, the pale green solid obtained gives on strong heating a solid H, and two gases I and J. These gases are compounds of non-metallic elements, one of which is in a different oxidation state in each compound. If J is passed into a solution of barium chloride there is a vigorous reaction and a white precipitate K is formed. A reacts with steam in an equilibrium reaction to give a solid M, which contains A in two different oxidation states, and the gas C; this reaction was at one time used industrially to make C. A reacts with gaseous HCl on heating to give K, a white solid, and C. Hydrated K is pale green. With chlorine, A gives a brown covalent solid L which sublimes on heating; aqueous solutions of the hydrate of L react with copper metal, and for that reason are used to etch printed-circuit boards in electronics. Solution B gives a dirty-green precipitate D if sodium hydroxide is added; this precipitate remains in excess sodium hydroxide. The same reaction is seen with the addition of ammonia. If D is allowed to stand in air it forms a foxy-red compound E, which is also obtained if sodium hydroxide solution is added to solutions of L. Acidified solutions of B decolourise potassium manganate(VII) solution giving the manganesecontaining ion N as one of the products. Identify all of the substances A N, and deduce as much as you can about the processes occurring. The colours involved in this reaction scheme should suggest that A is iron. With dilute sulphuric acid iron gives a pale green solution of iron(II) sulphate B, and hydrogen, C: A B + C: Fe + H2SO4 FeSO4 + H2 The pale green ion is [Fe(H2O)6]2+.

If solution B is allowed to crystallise, the iron(II) sulphate (also called green vitriol) gives iron(III) oxide H on strong heating, and sulphur dioxide (sulphur(IV) oxide) I and sulphur trioxide (sulphur(VI) oxide) J: B H + I + J: 2FeSO4 Fe2O3 + SO2 + SO3. The iron(III) oxide formed is a very fine powder, and is used as a polishing powder in the jewellery trade. It is sometimes called jewellers rouge.

If J is passed into a solution of barium chloride there is a vigorous reaction since sulphuric acid is formed rather violently from sulphur trioxide and water. That is why, in the Contact Process, the sulphur trioxide is absorbed in concentrated sulphuric acid and the mixture then diluted. The white precipitate K is barium sulphate: J K: SO3 + H2O 2H+ + SO42- (but see my article on the pH of sulphuric acid); followed by Ba2+ + SO42- BaSO4.

Iron reacts with steam in an equilibrium reaction to give tri-iron tetroxide M, which contains iron in oxidation states (+2) and (+3); Fe2O3.FeO; and hydrogen, C. This reaction was at one time used industrially to make hydrogen. The iron oxide formed was returned to the blast furnace. A M + C: 3Fe + 4H2O Fe3O4 + 4H2

With gaseous HCl on heating iron gives white K, anhydrous iron(II) chloride, and hydrogen: A K: Fe + 2HCl FeCl2 + H2

Hydrated iron(II) chloride is pale green. With chlorine on heating iron gives brown covalent iron(III) chloride L which sublimes on heating: A L: 2Fe + 3Cl2 2FeCl3

Aqueous solutions of iron(III) chloride react with copper metal to give iron(II) ions and copper(II) ions, and for that reason are used to etch printed-circuit boards in electronics: 2 [Fe(H2O)6]3+ + Cu + 6H2O 2 [Fe(H2O)6]2+ + [Cu(H2O)6]2+

The solution of iron(II) ions, B gives a dirty-green precipitate of iron(II) hydroxide D if sodium hydroxide is added; this precipitate remains in excess sodium hydroxide since it is not

amphoteric. The same reaction is seen with the addition of ammonia, the latter acting simply as an alkali. B D: [Fe(H2O)6]2+ + 2OH- Fe(OH)2 + 6H2O

If D is allowed to stand in air it forms a foxy-red compound E, which is iron(III) hydroxide produce by air oxidation of iron(II) hydroxide. This is also obtained if sodium hydroxide solution is added to solutions of L: L E: [Fe(H2O)6]3+ + 3OH- Fe(OH)3 + 6H2O

Acidified solutions of iron(II) ions decolourise potassium manganate(VII) solution being oxidised to iron(III) and giving the hexaquamanganese(II) ion N also: B F + N 5[Fe(H2O)6]2+ + 8H+ + MnO4- 5[Fe(H2O)6]3+ + Mn2+ + 4H2O