Heat: all ammonium salts decompose on heating; ammonium nitrate may explode.

Amm onium chloride and sulphate give products that recombine on cooling, so that the salts apparently sublime. NH4Cl(s) NH3(g) + HCl(g) NH4NO3(s) N2O(g) + 2H2O(g) 2(NH4)2SO4(s) 2NH3(g) + SO3(g) + H2O(g) Ammonium dichromate(VI) decomposes spectacularly on ignition in a reaction that is oxidation of the cation by the anion; the initially orange solid gives a fluf fy green product of much larger volume: (NH4)2Cr2O7(s) N2(g) + Cr2O3(s) + 4H2O(g) Alkalis (sodium hydroxide, calcium hydroxide) liberate ammonia from ammonium sal ts on warming with the solution, or even from a mixture of the solids. This is b ecause OH- is a stronger base than ammonia, so removes a hydrogen ion from the a mmonium ion: NH4+(aq) + OH-(aq) NH3(g) + H2O(l) The test solution is warmed with sodium hydroxide solution and the vapours teste d with moist red litmus paper. It is important to test the vapours immediately h eating begins, since the ammonia is lost very quickly and by the time the soluti on boils it may well have all gone. Chloride ClLinks AgCl, PbCl2, Hg2Cl2 and CuCl are insoluble in water. ______________________________

Concentrated sulphuric acid liberates steamy acidic fumes of HCl from solid chlo rides: NaCl(s) + H2SO4(l) " NaHSO4(s) + HCl(g) Silver nitrate solution added to a solution of a chloride that has been acidifie d (test with blue litmus paper) with dilute nitric acid gives a white precipitat e of silver chloride. The precipitate is readily soluble in dilute ammonia or in sodium thiosulphate solution: Ag+(aq) + Cl-(aq) " AgCl(s) AgCl(s) + 2NH3(aq) " [Ag(NH3)2]+(aq) + Cl-(aq) AgCl(s) + 2S2O32-(aq) " [Ag(S2O3)2]3-(aq) + Cl-(aq) Acidification with nitric acid is necessary to eliminate carbonate or sulphite, both of which interfere with the test by giving spurious precipitates. Concentrated solutions of sulphates can give a precipitate of silver sulphate in this test; its appearance is wholly different from AgCl. The latter is truly wh ite; the sulphate is a pearly white, rather like pearlescent nail varnish. Sulphate SO42BaSO4, SrSO4 and PbSO4 are insoluble; CaSO4 is sparingly soluble. Barium chloride solution added to the test solution acidified with dilute hydroc hloric acid gives a white precipitate of barium sulphate: Ba2+(aq) + SO42-(aq) BaSO4(s) HSO4- does the same thing with barium ions; however the original test solution w ould then be very acidic, so that should be tested for. The addition of HCl destroys any carbonate or sulphite ions present so prevents the spurious positive result due to the precipitation of these barium salts. Bar ium nitrate solution can be used instead of barium chloride. 18.2 Lead ethanoate solution gives a precipitate of white lead sulphate: Pb2+(aq) + SO42-(aq) PbSO4(s) Nitrate NO3Since all nitrates are water soluble, there is no precipitation reaction for thi s ion. Solid nitrates decompose on heating; those of group 1 (except Li) give the nitri te and oxygen; 2NaNO3(s) " 2NaNO2(s) + O2(g) All others give the metal oxide, nitrogen dioxide, and oxygen. A brown gas is em

itted that re-lights a glowing splint: 2Pb(NO3)2(s) " 2PbO(s) + O2(g) + 2NO2(g) Nitrate ions are reduced to ammonia by boiling with aluminium or with Devarda s Allo y in sodium hydroxide solution. Devarda s Alloy contains aluminium, zinc and copper. Since ammonium ions also give ammonia with NaOH, the test solution must be boil ed with NaOH and the vapour tested for ammonia; if present heating must continue until all the ammonia has gone. The mixture is then cooled, Devarda s Alloy (or a p iece of aluminium foil) added, and the mixture re-heated. A gas that turns moist red litmus paper blue indicates nitrate in the original solution: 3NO3-(aq) + 8Al(s) + 18H2O(l) + 21 OH-(aq) " 8[Al(OH)6]3-(aq) + 3NH3(g) Not an equation to be remembered! ________________________________________ Carbonate CO32Only the alkali metal and ammonium carbonates are water soluble. Some carbonates (e.g. zinc, copper(II)) are basic carbonates and contain a proportion of the hy droxide in their structure. Heating decomposes all but the alkali and alkaline earth metal carbonates (at Bu nsen temperatures) giving the oxide and carbon dioxide: CuCO3(s) " CuO(s) + CO2(g) Dilute hydrochloric acid gives vigorous effervescence with carbonates, evolving carbon dioxide: CO32-(aq or s) + 2H+(aq) " H2O(l) + CO2(g) Bicarbonates also give this effervescence. The reaction of carbonates with acid is exothermic; bicarbonates react endothermically. Sulphite SO32Sulphurous acid is considerably stronger than carbonic acid, so sulphites do not give the effervescence that is characteristic of carbonates when dilute acid is added. Dilute hydrochloric acid on warming with a sulphite evolves sulphur dioxide; thi s turns acidified potassium dichromate(VI) solution (or paper) green: SO32-(aq) + 2H+(aq) " H2O(l) + SO2(g) Barium chloride solution gives a white precipitate of barium sulphite; addition of dilute hydrochloric acid causes the precipitate to dissolve without effervesc ence: SO32-(aq) + Ba2+(aq) " BaSO3(s) Solubility The following are insoluble (or nearly so) in water: Halides: Pb2+, Ag+ Sulphates: Ba2+, Sr2+, Ca2+, Pb2+ Carbonates: all except those of the alkali metals. Aluminium carbonate does not exist. The action of sodium hydroxide solution To a solution of the test substance, sodium hydroxide solution is added drop by drop until it is in excess (test with red litmus paper). Some solutions may be a cidic to begin with (test the original solution with blue litmus paper); in such cases nothing will happen until the acid has all been neutralised. The chemistr y of the tests with sodium hydroxide and with ammonia is covered in more detail in the cation analysis page. White precipitate insoluble in excess NaOH: Mg2+, Ca2+. White precipitate soluble in excess NaOH: Al3+, Zn2+, Pb2+. Blue precipitate turning black on warming: Cu2+ Light green precipitate insoluble in excess NaOH: Ni2+ Dirty-green precipitate, turning brown on standing: Fe2+ Greyish-green precipitate soluble in excess NaOH to a deep green solution: Cr3+. Foxy red (rust coloured) precipitate: Fe3+. Beige precipitate turning brown on standing: Mn2+ Blue precipitate (turning grey) from a red solution: Co2+

________________________________________ The action of aqueous ammonia solution To a solution of the test substance, ammonia solution is added drop by drop unti l it is in excess (test with red litmus paper). Some solutions may be acidic to begin with (test the original solution with blue litmus paper); in such cases no thing will happen until the acid has all been neutralised. White precipitate insoluble in excess ammonia: Mg2+, Ca2+, Al3+, Pb2+. White precipitate soluble in excess ammonia: Zn2+. Blue precipitate turning to a deep blue solution with excess ammonia: Cu2+. Green precipitate soluble in excess ammonia to give pinkish solution: Ni2+. Dirty-green precipitate, turning brown on standing: Fe2+. Green precipitate insoluble in excess ammonia: Cr3+. Foxy red (rust coloured) precipitate: Fe3+. Beige precipitate turning brown on standing: Mn2+. Blue precipitate from a red solution giving a blue solution with excess ammonia: Co2+. ________________________________________ The action of dilute hydrochloric acid A little of the substance is added to about 5cm3 of dilute HCl. If there is no r eaction warm gently. Test any gases evolved. CO2 evolved with vigorous effervescence: Carbonate or bicarbonate. Note that th e only solid bicarbonates are those of group 1 metals. NO2 (brown) evolved: Nitrite. The solution will be pale blue. SO2 evolved: Sulphite. Ethanoic acid evolved (smell of vinegar): Ethanoate. ________________________________________ The action of concentrated sulphuric acid A little of the solid substance is added to about 2cm3 of concentrated sulphuric acid (CARE! Corrosive). If there is no reaction the mixture is warmed cautiousl y. HCl evolved as steamy acidic fumes: Chloride. Brown fumes: HBr + Br2 + SO2 from a bromide these will turn a drop of silver nitra te on a glass rod cloudy. or NO2 from a nitrate or nitrite. Purple fumes, brown mess, smell of bad eggs: HI + I2 + H2S from an iodide. CO and CO2 evolved: Ethanedioate. Tests for gases These require careful technique. If the gas is to be collected it can be done by sucking the gas into a teat pipette. Hydrogen: Usually ignites with a squeaky pop. A very unlikely product since it i s only obtained from reactive metals or from hydrides. The pop is the explosion caused by hydrogen burning in the oxygen which usually contaminates it. Oxygen: Relights a glowing splint - an example of increased reaction rate due to higher reagent concentration. This sometimes pops but not in the same squeaky w ay that hydrogen does. Carbon monoxide: Burns with a blue flame but does not explode. Carbon dioxide: Turns limewater milky, or, better, gives a white precipitate wit h limewater. Sulphur dioxide: When passed into acidified potassium dichromate solution turns it from orange to green. The chromium(VI) is reduced to green Cr(III), and the S O2 is oxidised to sulphate. Halogen hydrides (or hydrogen halides): Turn a drop of silver nitrate on a glass rod cloudy: HCl white, HBr cream, HI yellow. Give a white smoke with ammonia fu mes. Chlorine: Turns blue litmus red, then bleaches it. Turns moist starch-iodide pap er blue-black (because of oxidation of iodide to iodine). Gives a yellow solutio n of bromine with aqueous sodium bromide, and a darker yellow or brown solution

of iodine with aqueous sodium iodide. On shaking with hexane the solutions colou r the hexane brown or purple respectively. Bromine (brown fumes): Reddens and then slowly bleaches blue litmus paper. Turns fluorescein paper scarlet. Liberates iodine from aqueous sodium iodide. Iodine (violet fumes): Turns starch-iodide paper blue-black. Gives a cream preci pitate with silver nitrate solution because of formation of bromide ions in aque ous bromine. Nitrogen dioxide (brown fumes): Turns moist starch iodide paper blue. Does not a ffect silver nitrate solution. Ammonia: Turns red litmus paper blue. Gives white smoke with concentrated hydroc hloric acid vapours.