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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) ï ¢ NH3(g) + HCl(g) NH4NO3(s) ï ¢ N2O(g) + 2H2O(g) 2(NH4)2SO4(s) ï 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) ï ¢ 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) ï ¢ 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) ï ¢ 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) ï ¢ 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

Ca2+. turning brown on standing: Fe2+ Greyish-green precipitate soluble in excess NaOH to a deep green solution: Cr3+. the test solution must be boil ed with NaOH and the vapour tested for ammonia. Ca2+. White precipitate soluble in excess NaOH: Al3+. zinc. The mixture is then cooled. Some carbonates (e. Blue precipitate turning black on warming: Cu2+ Light green precipitate insoluble in excess NaOH: Ni2+ Dirty-green precipitate. Pb2+. so sulphites do not give the effervescence that is characteristic of carbonates when dilute acid is added. zinc and copper. The action of sodium hydroxide solution To a solution of the test substance.g. Sulphite SO32Sulphurous acid is considerably stronger than carbonic acid. copper(II)) are basic carbonates and contain a proportion of the hy droxide in their structure. White precipitate insoluble in excess NaOH: Mg2+. if present heating must continue until all the ammonia has gone. The reaction of carbonates with acid is exothermic. Sr2+. Aluminium carbonate does not exist. Foxy red (rust coloured) precipitate: Fe3+. Some solutions may be a cidic to begin with (test the original solution with blue litmus paper). Devardaâ s Alloy (or a p iece of aluminium foil) added. bicarbonates react endothermically. 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+. Dilute hydrochloric acid on warming with a sulphite evolves sulphur dioxide. 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. evolving carbon dioxide: CO32-(aq or s) + 2H+(aq) " H2O(l) + CO2(g) Bicarbonates also give this effervescence.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 Devardaâ s Allo y in sodium hydroxide solution. Beige precipitate turning brown on standing: Mn2+ Blue precipitate (turning grey) from a red solution: Co2+ . in such cases nothing will happen until the acid has all been neutralised. sodium hydroxide solution is added drop by drop until it is in excess (test with red litmus paper). Since ammonium ions also give ammonia with NaOH. Ag+ Sulphates: Ba2+. 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. 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. Zn2+. Devardaâ s Alloy contains aluminium. The chemistr y of the tests with sodium hydroxide and with ammonia is covered in more detail in the cation analysis page. and the mixture re-heated. Pb2+ Carbonates: all except those of the alkali metals.

Al3+. Ca2+. Carbon dioxide: Turns limewater milky. Green precipitate insoluble in excess ammonia: Cr3+. Green precipitate soluble in excess ammonia to give pinkish solution: Ni2+. Gives a yellow solutio n of bromine with aqueous sodium bromide. and the S O2 is oxidised to sulphate. Tests for gases These require careful technique. or. NO2 (brown) evolved: Nitrite. A very unlikely product since it i s only obtained from reactive metals or from hydrides. Foxy red (rust coloured) precipitate: Fe3+. The pop is the explosion caused by hydrogen burning in the oxygen which usually contaminates it. turning brown on standing: Fe2+. Beige precipitate turning brown on standing: Mn2+. ammonia solution is added drop by drop unti l it is in excess (test with red litmus paper). Dirty-green precipitate. The solution will be pale blue. HBr cream. If there is no reaction the mixture is warmed cautiousl y. SO2 evolved: Sulphite. Purple fumes. Sulphur dioxide: When passed into acidified potassium dichromate solution turns it from orange to green. Give a white smoke with ammonia fu mes. Ethanoic acid evolved (smell of vinegar): Ethanoate. HI yellow. White precipitate soluble in excess ammonia: Zn2+. CO2 evolved with vigorous effervescence: Carbonate or bicarbonate. Turns moist starch-iodide pap er blue-black (because of oxidation of iodide to iodine). and a darker yellow or brown solution . If the gas is to be collected it can be done by sucking the gas into a teat pipette. Halogen hydrides (or hydrogen halides): Turn a drop of silver nitrate on a glass rod cloudy: HCl white. ________________________________________ The action of dilute hydrochloric acid A little of the substance is added to about 5cm3 of dilute HCl. Note that th e only solid bicarbonates are those of group 1 metals. Blue precipitate from a red solution giving a blue solution with excess ammonia: Co2+. The chromium(VI) is reduced to green Cr(III).________________________________________ The action of aqueous ammonia solution To a solution of the test substance. Hydrogen: Usually ignites with a squeaky pop. White precipitate insoluble in excess ammonia: Mg2+. Oxygen: Relights a glowing splint . Blue precipitate turning to a deep blue solution with excess ammonia: Cu2+. smell of bad eggs: HI + I2 + H2S from an example of increased reaction rate due to higher reagent concentration. Test any gases evolved. Some solutions may be acidic to begin with (test the original solution with blue litmus paper). If there is no r eaction warm gently. better. gives a white precipitate wit h limewater. 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. then bleaches it. brown mess. Brown fumes: HBr + Br2 + SO2 from a bromide â these will turn a drop of silver nitra te on a glass rod cloudy. CO and CO2 evolved: Ethanedioate. HCl evolved as steamy acidic fumes: Chloride. or NO2 from a nitrate or nitrite. in such cases no thing will happen until the acid has all been neutralised. Chlorine: Turns blue litmus red. Pb2+. ________________________________________ The action of concentrated sulphuric acid A little of the solid substance is added to about 2cm3 of concentrated sulphuric acid (CARE! Corrosive).

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