Flame test The substance is moistened with conc. HCl, and the mixture, on a platinum wire is shown in the edge of the non-luminous Bunsen flame. Flame Colour Inference Golden yellow Na Lilac (violet) K Brick – red Ca Crimson Sr Apple green Ba Bluish green Cu Green Borates Livid blue Pb, Sb, Bi Dil. Acid group To about 5 mg of the substance add about 0.5 ml of dil. HCl. Observe the reaction in the cold and then heat it on a water bath. Observation 1. Brisk effervesce, the gas turns lime/Baryta water milky Inference Carbonate is Present. 2. Colourless gas (SO2) with the smell of burning sulphur .The gas turns Sulphite is Present. a filter paper dipped in acidified potassium dichromate green. 3. Colourless gas with the odour of rotten eggs (H2S) is evolved. The gas Sulphide is turns lead acetate paper black and Present. cadmium acetate paper yellow. 4. Vineger smell. Red coloration/ppt with neutral ferric chloride. Acetate is 5. Mix 20 mg of the substance with 1ml of ethyl alcohol and 5 drops of con. Present. H2SO4, Heat in a hot water rack for 10 minutes, and pour into 2 ml of Na2CO3 solution. Fruity odour Addition of Conc. H 2SO4 + MnO2, heat Observation Inference 1. Greenish yellow pungent smelling gas (HCl) which fumes in Chloride is moist air. Dense white fumes (NH4Cl) with a drop of ammonia Present. on a glass rod 2. Reddish brown fumes (Br2) are evolved. 3. violet vapours (I2) are evolved. 4.On warming, brown gas (NO2)With characteristic smell is evolved. The brown colour is deepened by the addition of copper turnings. Bromide is Present. Iodide is Present. Nitrate is Present. Silver nitrate group Add silver nitrate to Neutralized sodium carbonate extract 1 2 3 A curdy white precipitate (AgCl), insoluble in dil.HNO3, but soluble in ammonia solution. A pale yellow precipitate (AgBr), insoluble in dil. HNO3, but sparingly soluble in ammonia solution. A yellow precipitate, insoluble in both dil. HNO3 and ammonium solution. Chloride is confirmed. Bromide is confirmed. Iodide is confirmed. Test for Bromide and Iodide: To the substance in dil. HNO3 add drops of KMnO4 solution until the pink colour persists. Add CCl4 and shake. Reddish brown colouration of CCl4 layer Bromide is confirmed. Violet colouration of CCl4 layer. Iodide is confirmed. Nitrate : Brown ring test The sodium carbonate extract is acidified with dil. H2SO4. An equal volume of freshly prepared FeSO4 solution is added. Holding the test-tube in an inclined position con. H2SO4 drops are added without shaking. A brown ring is formed at the junction of the two layers Nitrate is confirmed. Sulphate : BaCl2 test To the sodium carbonate extract add dil. HCl till no more CO2 is evolved. Add 1-2 ml of dil. HCl and BaCl2 solution. A white precipitate insoluble in dil. HCl is formed Sulphate is Confirmed Borate: Flame Test The substance is mixed with calcium flouride and con. H2SO4 to get a paste. Hold some of the paste on a platinum loop, just outside the base of the Bunsen flame. A green flame is formed Borate is confirmed. Phosphate : Amm. Molybdate test To the sodium carbonate extract add dil. HNO 3ill no more CO2 is evolved. Add 1-2 ml of amm. Molybdate. Warm. Yellow ppt Phosphate is confirmed. Oxalate Acidify the sodium carbonate extract with dilute acetic acid and add calcium chloride solution. White ppt. Divide the precipitate into two parts – •Add dilute HCl ppt dissolves •Add hot dil. H2 SO4 and potassium permanganate drop wise it gets decolourised Oxalate is confirmed Analysis of Cations •Preparation of the original solution A small quantity of the substance (15 mg) is treated with the following solvents in the given order. •Distilled water •dil.HCl, •dil.HNO3 •con.HCl •aqua regia (3 vol. con. HCl + 1 vol. con. HNO3). Observe the solubility in the cold, then heat to boiling. If any gases are formed, boil them off. Dissolve 50 to 100 mg of the substance in the suitable solvent and prepare the solution. This solution is often referred to as the original solution. Cations/ Groups / Group reagents Group Group reagent Cations Ppt formed I Dil. HCl Pb2+ , Ag Hg1+ , Chlorides II Dil. HCl + H S Pb2+ , Bi3+ , Cd2+ , Cu2+ , Sn2+ , As3+ , Sb3+ Sulphides III NH Cl + NH OH Fe3+ , Al3+ , Cr3+ Hydroxides IV NH Cl + NH OH + H S Co2+ , Ni2+ , Zn2+ , Mn2+ Sulphides V NH Cl + NH OH + NH CO Ca2+ , Ba2+ , Sr2+ Carbonates VI No group reagent Mg2+ , NH+ , K+ -- 1+ Separation of Cations into Groups To 1 ml of the original solution in a centrifuge tube, dil. HCl is added until precipitation, if any, is complete Centrifuge. Residue -1 White, may contain PbCl2, Hg2Cl2 or AgCl. Centrifugate-1 Heat on a water bath; pass H2S gas until the precipitation is complete. Centrifuge. Residue-2 Centrifugate-2 : (Eliminate the interfering anions if May necessary.Boil off H2S Add 3 drops of con.HNO3 and Contain boil.Add 100 mg solid ammonium chloride, heat on a Black:HgS, PbS, water bath. Add ammonia solution till alkaline, and CuS. add 2 drops excess. Warm. Stir. Centrifuge. Brown:Bi2S3. Residue-3: Centrifugate-3: Add 2 drops Yellow:CdS, May contain of NH3 solution. Warm. Pass Reddish-brown:Fe(OH)3 H2S to complete Group- Sb2S3,SnS2 Green:Cr(OH)3 precipitation. Centrifuge. Group – 2 1 White:Al(OH)3 Wash the residue present present Group 3 Present Separation of Cations into Groups Contd…. Residue-4: May contain Black: CoS, NiS Pink: MnS, White: ZnS Group 4 present Centrifugate-4: Place in a china dish. Acidify with dil. Acetic acid. Evaporate to a pasty mass. Add 5 drops of con.HNO3.Heat to dryness (till fumes stop)7 Dissolve the residue in 5 drops of dil. HCl and 1 ml water. Add (in testtube) 5 drops of 20% NH4Cl. Add NH4OH with shaking till alkaline. Add excess of 10% (NH4)2CO3 soln. Warm at 5060oC. Centrifuge. Wash. Residue -5 May contain White: BaCO3,SrCO3, CaCO3 Group 5 present Centrifugate-5: Evaporate to a pasty mass, add 0.5 ml con.HNO3. Heat to dryness White residueGroup-6 present Analysis of Group I Separation of group 1 cations: The Residue-1 is washed with cold water containing a few drops of dil. HCl, and centrifuged. To the residue, add 1 ml of hot water. Heat to boiling for 12 minutes. Centrifuge while hot. Transfer the centrifugate quickly to another test tube. Residue (Residue 1.1): White: May contain Hg2Cl2 Centrifugate (1.1) : May contain PbCl2. and AgCl. Wash with boiling water to remove the Divide into 3 parts. undissolved PbCl2.Treat the residue with 0.5 ml 1. Cool under tap – White ppt. warm dilute NH3 solution. Stir. Centrifuge. reappears . – Pb2+ is confirmed. Residue (1.2), Black:Hg + Centrifugate (1.2): May Hg (NH2) Cl. Hg22+ contain Ag (NH3)2Cl. Divide 2. Add 2 drops of potassium chromate – Yellow ppt. (PbCrO4).- Pb2+ is present. Dissolve the into 2 parts. confirmed. ppt. in aqua-regia, heat, 1. Add dil.HNO3. White divide into two parts. 3. Add 2 drops of KI solution –Yellow ppt. (AgCl) – Ag2+ is ppt. (PbI2).Boil the ppt. with water and 1. Add stannous chloride confirmed. a few drops of acetic acid and cool. - White grayish ppt. 2. Add KI solution- Yellow 2+ The ppt. dissolves on heating and Hg2 is confirmed. 2+ ppt. (AgI) –Ag is reappears as golden spangles on 2. Add drops of KI confirmed. cooling – Pb2+ is confirmed. solution- Red or Yellow ppt. Hg22+ is confirmed. Analysis of Group II A Residue-2A: May contain Hg2+, Pb2, - Bi 3+ , Cu2+ and Cd2+ Add 1.5 ml dil.HNO3. Warm and centrifuge. Residue Centrifugate-: May contain nitrates of Pb, Bi, Cu, and Cd. Add excess con.NH3 solution and centrifuge. Black: HgS, Residue May contain Bi3+ and Pb2+. Add 1ml Centrifugate: May contain Cu2+, NaOH solution. Warm. Centrifuge. and Cd2+. Wash with Residue May be Bi (OH)3 wash Centrifugate 1. a) solution is colourless - Cu2+ Water. Dissolve in 3 drops with water. Divide the May contain Pb is absent. con. HCl and 1 drop con. precipitate into 2 parts. (OH)4-. Acidify with HNO3. Heat. Divide into 2 b) Pass H2S gas through the 1. Add sodium stannite dil. Acetic acid. parts. solution. Yellow precipitate – Cd2+ reagent. Immediate Divide into 2 parts. is confirmed. 1. Add 2 drops blackening of precipitate. – 1. Add K2CrO4 SnCl2.White grey 3+ is present. Bi 2. a) Solution is blue – Cu2+ is 2+ solution Yellow precipitate. Hg is present. Divide into 2 parts 2. Dissolve in 3 drops of precipitate. Pb2+ is confirmed Conc.HNO3. Pour 1 drop of confirmed. 1. Add acetic acid in excess and 1 2. Add KI solution Red the solution in 5 ml waterdrop [K4 Fe (CN)6 ] solution. Red2. Add dil.H SO – precipitate. dissolving in 2 4 white turbidity- Bi 3+ is brown precipitate. Cu2+ is 2+ white precipitate. excess KI. Hg is confirmed. confirmed. Pb2+ is confirmed. confirmed. 3. Dilute the above solution. 2. Add KCN (poison) to discharge To one drop, on a spot plate, blue colour. Pass H2S. Yellow add a drop of Cinchonine – KI precipitate. Cd2+ is confirmed. reagent. Orange-red spot- Bi3+ is confirmed. Analysis of Group II B The centrifugate-2Amay contain Sb3+ and Sn2+ . Centrifuge. Wash the Residue. Reject washings. Treat the residue with 1ml conc. HCl. Warm on water bath for 3 minutes. Stir. Centrifuge. ResidueMay contain HgS. Black: It is tested for Hg as given in the Group 2 A. (Yellow precipitate. of As2O3 also appears here. Centrifugate- May contain HSbCl4 and H2SnCl6.Take small portions and test as under: 1. Add NH3 solution till just alkaline. Add 0.3 gms of oxalic acid. Pass H2S for 30 seconds. – Orange precipitate. (Sb2S3)-Sb 3+ is present. 2. To 2 drops of the solution on a spot plate, add a minute crystal of NaNO2 Stir. Add 2 drops of Rhodamine-B reagent. Violet colouration- Sb 3+ is present. 3. Treat 0.3ml of the solution with 10mg of Mg powder. Add 2 drops of FeCl3 solution, 3 drops of 5% tartaric acid solution, 2 drops of dimethyl glyoxime reagent, then dil.NH3 solution until basic. Red colouration. Sn4+ is present. ANALYSIS OF GROUP III The group III precipitate. (Residue-3) may contain Fe3, Al3+ and Cr3+. Dissolve the precipitate in 2ml of NaOH solution in a boiling tube, add 1ml of 3% H2O2. Boil gently and centrifuge. Residue: May Contain Fe3 .Dissolve the precipitate in 0.5ml of dil.HNO3. Add potassium ferrocyanide – Deep blue precipitate.-Fe3+ is present Confirmatory test for Fe2+And Fe3+ 1. To the original solution add Centrifugate: May contain NaAlO2 (colourless), and NaCrO4 (yellow).(Test only for Al if the solution is colourless. Test portions as under. 1. Add dil. HCl till acidic. Add NH3 solution. till just alkaline, add 1 drop more. Warm. White Gelatinous precipitate of Al(OH)3. .Al3+ is present. 2. Centrifuge the above precipitate. Dissolve in dil. HCl, add ammonium thiocyanate solution. 0.3ml ammonium acetate solution and1 drop of aluminon a)No colouration.Fe2+ is confirmed . 3+ b)Deep red colouration. Fe3+ is confirmed. reagent A bright red precipitate. Al is confirmed. 3. To a drop of the centrifuge-3.1solution on a spot plate, add 2. To the original solution Potassium 1drop of 1% aqueous alizarin-S. Add drops of acetic acid until ferrocyanide solution is added. violet colour appears. Add a few more drops of acetic acid. A a)Deep blue colour. Fe3+ is confirmed. red precipitate or colouration appears. Al3+ is confirmed. b)Pale blue colour. Fe2+ is confirmed. 4.Acidify with dil. acetic acid. Add 1 drop of lead acetate solution. Yellow precipitate.(PbCrO4).Cr3+ present. 5. Acidify with dil. HNO3, cool, add 0.5ml of amyl alcohol or ether and 2 drops of 3% H2O2.Shake. Allow to stand. The organic layer becomes blue which is unstable. Cr3+ is confirmed. ANALYSIS OF GROUP IV The group IV precipitate (Residue-4) may contain Co2+, Ni2+, Mn absent. Stir the precipitate in the cold, with very dil. HCl. Centrifuge. 2+ and Zn2. If not black, Co2+ and Ni2+ are Residue: May Contain Co2+and Ni2+. Centrifugate: May contain Mn2+ and Zn2+. Boil off to expel H2S Cool. Add excess Dissolve the precipitate. in 5 drops of of NaOH solution until basic and 4 drops of 3% H2O2 solution. Warm for 3 aquaregia. Divide into 3 parts. minutes. Centrifuge. 1. Add amyl alcohol and 50mg solid Residue-4.2: May contain Mn 2+. Centrifugate-4.2: May contain Zn2. Divide into 3 NH4SCN. Shake. Blue colouration in Dissolve in 1ml dil.HNO3. Divide parts. the alcohol layer – Co2+ is confirmed. into 2 parts. 1. Pass H2S. White precipitate. (ZnS). Zn2+ is 2. Add drops of 1% alcoholic alpha- 1. Add 2 drops of 3% H2O2. confirmed. nitroso-betanaphthol. Reddish Warm to decompose excess 2. Just acidify with dil. H2SO4, add 5 drops of brownprecipitate. Co2+ is confirmed. H2O2. Cool. Add 50 mg NaBiO3. 0.1% CuSO4 solution and 5 drops of ammonium Shake. Allow to stand. The mercury thiocyanate reagent. Stir. Violet 3. Add 1 drop of NH4Cl solution. Make it faintly alkaline with NH3 solution turns purple – Mn 2+is precipitate. Zn2+ is confirmed. solution. Add 3-5 drops of dimethyl confirmed. 3. Just acidify with dil.H2SO4. Add a drop of dil. glyoxime reagent. Redprecipitate. 2. Take the other part in a boiling cobalt nitrate solution, 0.5ml of ammonium 2+ Ni is confirmed. tube with 0.5 ml H2O. Add 2 mercury-thiocyanate reagent. Stir. Pale blue drops of 3% H2O2. Boil to precipitate. decompose excess H2O2. Cool. Zn2+ is confirmed. Add 0.5ml con.HNO3 and 250mg PbO2. Boil. Allow to stand – A purple solution is formed. Mn2+ is confirmed. ANALYSIS OF GROUP V The group V precipitate. (Residue-5) may contain Ba2+, Ca2+ and Sr 2+. Dissolve the precipitate in 1 ml of dil. acetic acid . Warm. Divide into three parts and test as follows. Part 1 Add a few drops of K2Cr2O7 Yellow ppt of BaCrO4. Ba2+ is confirmed. Dissolve the residue in a few drops of conc. HCl, Apply flame test. Yellowish green flame. Ba2+ is confirmed. Part 2 To 1ml of the solution add1ml of saturated ammonium sulphate solution followed by 0.1 g sodium thiosulphate. Heat on water bath for 5 minutes. White ppt. of SrSO4, Sr2+ is present. Add a few drops of conc. HCl to the ppt, apply flame test. Crimson flame. Sr2+ is confirmed. Part 3 Divide into two parts 1. Add NH3 solution to get the smell of ammonia. Add ammonium oxalate solution. Warm. White precipitate. Ca2+ is confirmed. 2. The other portion is evaporated to a pasty mass. Add 1 drop of conc. HCl. Apply flame test. Brick-red flame. Ca2+ is confirmed. ANALYSIS OF GROUP VI The centrifugate from Group VI is evaporated to dryness. A white residue is obtained. Group VI cations are present. Dissolve in a few drops of dil. HCl. Add 1ml of water. Divide into 3 parts. 1. Add 3 drops NH4Cl, and NH4OH till alkaline. Add 4 drops of Na2HPO4. White precipitate. Mg2+ confirmed. 2. Add 2 drops of Magneson reagent and NaOH solution drops till alkaline. A blue precipitate. Mg2+ is confirmed. 3. Add a few drops of 2% oxine solution ( 8 – hydroxyquinoline). Warm. Pale yellow precipitate of Mg oxinate. Mg 2+ Present.