ANIONS: Chloride ClAgCl, 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. Bromide BrAgBr, PbBr2, Hg2Br2 and CuBr are insoluble in water. Concentrated sulphuric acid gives a mixture of hydrogen bromide, bromine and sul phur dioxide with solid bromides; the HBr produced is oxidised by sulphuric acid . The mixture evolves steamy brownish acidic fumes: NaBr(s) + H2SO4(l)----> " NaHSO4(s) + HBr(g) 2HBr + H2SO4 ----->" Br2 + SO2 + 2H2O Silver nitrate solution added to a solution of a bromide that has been acidified (test with blue litmus paper) with dilute nitric acid gives a cream precipitate of silver bromide. The precipitate is readily soluble in concentrated ammonia: Ag+(aq) + Br-(aq)--------> " AgBr(s) AgBr(s) + 2NH3(aq) ------->" [Ag(NH3)2]+(aq) + Br-(aq) Acidification with nitric acid is necessary to eliminate carbonate or sulphite, both of which interfere with the test by giving spurious precipitates. Oxidising agents oxidise bromide to bromine, which is yellow or orange in aqueou s solution. Bromine can be extracted from the solution by shaking with an immisc ible organic solvent, for example hexane, the organic layer then turning orange. A suitable oxidising agent is sodium chlorate(I); this is added to the test solu tion, followed by a little dilute hydrochloric acid and a few cm3 of hexane: OCl-(aq) + 2H+(aq) + 2Br-(aq) ----->" Br2(aq) + Cl-(aq) + H2O(l)

Iodide IAgI, PbI2, Hg2I2 and CuI are insoluble in water. Concentrated sulphuric acid gives a mixture of hydrogen iodide, iodine, hydrogen sulphide, sulphur and sulphur dioxide when added to solid iodides; the HI produ ced is oxidised by sulphuric acid. The mixture evolves purple acidic fumes, turn s to a brown slurry, and is a mess: NaI(s) + H2SO4(l) ---->" NaHSO4(s) + HI(g) 2HI + H2SO4-----> " I2 + SO2 + 2H2O 6HI + H2SO4 ----->" 3I2 + S + 4H2O 8HI + H2SO4 ------>" 4I2 + H2S + 4H2O There are no state symbols in these equations because the mixture is such a mess , and is more sulphuric acid than water. Silver nitrate solution added to a solution of an iodide that has been acidified (test with blue litmus paper) with dilute nitric acid gives a yellow precipitat e of silver iodide. The precipitate is insoluble even in concentrated ammonia: Ag+(aq) + I-(aq) ------>" AgI(s) Acidification with nitric acid is necessary to eliminate carbonate or sulphite, both of which interfere with the test by giving spurious precipitates. Oxidising agents oxidise iodide to iodine, which is yellow or orange in aqueous solution. Iodine can be extracted from the solution by shaking with an immiscibl e organic solvent, for example hexane, the organic layer then turning purple. A suitable oxidising agent is sodium chlorate(I); this is added to the test solu tion, followed by a little dilute hydrochloric acid and a few cm3 of hexane: OCl-(aq) + 2H+(aq) + 2Ir-(aq)----> " I2(aq) + Cl-(aq) + H2O(l) Lead ethanoate or lead nitrate solutions give a bright yellow precipitate of lea d(II) iodide with iodides: Pb2+(aq) + 2I-(aq) ---->" PbI2(s) The colour of lead(II) iodide comes from interactions in the lattice; dissolving the salt in boiling water gives a colourless solution which deposits glittering yellow plates on cooling. Solutions of copper(II) salts give a brown mixture containing iodine and copper( I) iodide when added to solutions of iodides. Addition of sodium thiosulphate so lution decolourises the iodine and leaves pinkish-cream copper(I) iodide as a pr ecipitate. 2Cu2+(aq) + 4I-(aq) -------->" 2CuI(s) + I2(aq) 2S2O32-(aq) + I2(aq) -->" 2I-(aq) + S4O62-(aq) This reaction is the basis for the volumetric estimation of copper; the iodine l iberated from a known amount of a copper(II) solution is titrated with standard sodium thiosulphate solution.

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) 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 Al loy in sodium hydroxide solution. Devarda s Alloy contains aluminium, zinc and cop

per. Since ammonium ions also give ammonia with NaOH, the test solution must be boiled with NaOH and the vapour tested for ammonia; if present heating must cont inue until all the ammonia has gone. The mixture is then cooled, Devarda s Alloy ( or a piece 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. Hydrogen carbonate (bicarbonate) HCO3Only the alkali metal and ammonium bicarbonates are obtainable as solids; group 2 bicarbonates exist only in solution. Calcium chloride solution on addition to a bicarbonate solution gives no precipi tate since calcium bicarbonate is soluble; this distinguishes it from carbonate, which does give a precipitate. On heating the calcium chloride/bicarbonate mixt ure a white precipitate appears since the bicarbonate decomposes to carbonate: Ca2+(aq) + 2HCO3-(aq)----> " CaCO3(s) + CO2(g) + H2O( cations: Because of chemical properties, cations are usually divided into five groups. Ea ch group has a common reagent which can be used to separate them from the soluti on. The separation has to be done in order, as, for example, some ions of 1st gr oup can also react with 2nd group reagent, so that the solution must not have an y ions left from previous groups to obtain meaningful results. Keep in mind that the division and precise details of separating into groups var y slightly from one source to another; given below is one of the commonly used s chemes. 1st analytical group of cations 1st analytical group of cations consists of ions which form insoluble chlorides. As such, the group reagent to separate them is hydrochloric acid, usually used at concentration of 1 2 M. Concentrated HCl must not be used, because it forms a s

oluble complex ion - [PbCl4]2- with Pb2+. Consequently the Pb2+ ion would go und etected The most important cations in 1st group are Ag+, Hg22+, Pb2+. The chlorides of t hese elements cannot be distinguished from each other by their colour - they are all white solid compounds. PbCl2 is soluble in hot water, and can therefore be differentiated easily. To distinguish between the other two, ammonia is used as a reagent. While AgCl is soluble in ammonia (due to the formation of the complex ion [Ag(NH3)2]+ion), Hg2Cl2 gives a black precipitate of chloro-mercuric amide with elemental mercury. Further, AgCl is reduced to silver under light and chang es its colour to violet. PbCl2 is far more soluble than the chlorides of the other two ions, especially i n hot water. Therefore, HCl in concentrations which completely sedimentize Hg22+ and Ag+, may not be sufficient to do the same to Pb2+ and higher concentrations can't be used for the aforementioned reasons. Thus, a filtrate obtained after f irst group analysis of Pb2+ contains an appreciable concentration of this cation , enough to give the test of the second group, viz. formation of an insoluble su lphide. For this reason, Pb2+ is usually also included in the 2nd analytical gro up 2nd analytical group of 2nd analytical group of ic solution. Cations in +, Sb5+, Sn2+, Sn4+ and the first group. cations cations are ions of which sulfides are insoluble in acid the 2nd group include: Cd2+, Bi3+, Cu2+, As3+, As5+, Sb3 Hg2+. Pb2+ is usually also included here in addition to

The reagent can be any substance which gives S2- ions in such solutions; most co mmonly used are H2S (at 0.2-0.3 M), AKT (at 0.3-0.6 M). The test with the sulphi de ion must be carried out in the presence of dilute HCl. Its purpose is to keep the sulfide ion concentration at a required minimum, so as to allow the precipi tation of 2nd group cations alone. If dilute acid is not used, the advanced prec ipitation of 4th group cations (if present in solution) may occur, thus leading to wrong results. Acids beside HCl are rarely used. Sulfuric acid may lead to th e precipitation of 4th group cations, while nitric acid directly reacts with the sulfide ion (reagent), forming colloidal sulfur. The precipitates of these cations are almost indistinguishable, except for Cd2+, which gives a yellow precipitate. All the precipitates, except for HgS, are sol uble in dilute mineral acids. HgS is soluble only in aqua regia, and this can be used to separate it from the rest. The action of ammonia is also useful in diff erentiating the cations. CuS dissolves in ammonia forming an intense blue soluti on, while CdS dissolves forming a colourless solution. The sulfides of As3+, As5 +, Sb3+, Sb5+, Sn2+, Sn4+ are soluble in yellow ammonium sulfide. 3rd analytical group of cations 3rd analytical group of cations includes ions which sulfides are insoluble in ba sic solution. The reagents are similar to these of the 2nd group, but separation must be done at pH of 8 9. If needed, a buffer solution can be used to keep it at this level. Cations in the 3rd group are, among others: Zn2+, Ni2+, Co2+, Mn2+, Fe2+, Fe3+, Al3+ and Cr3+. 4th analytical group of cations Ions in 4th analytical group of cations form carbonates that are insoluble in wa ter. The reagent usually used is (NH4)2CO3 (at around 0.2 M), the pH should be n eutral or slightly basic.

Caution should be taken to properly separate all lower analytical groups beforeh and, as many of cations in previous groups also form insoluble carbonates. Most important ions in the 4th group: Ba2+, Ca2+, and Sr2+. After separation, th e easiest way to distinguish them is by testing flame colour: barium makes flame yellow-green, calcium orange-red and strontium deep red. 5th analytical group of cations Cations which are left after carefully separating previous groups are considered