QUALITATIVE ANALYSIS Qualitative Inorganic Analy (Qualitative inorganic analysis involves the detection of cations (basic radicals) and anions (acid radicals) present {nan inorganic compound or a mixture of inorganic comopounds. Fora systematic study, qualitative analysis may be studied in the following parts: (A) Dry tests for inorganie compounds (B) Confirmatory tests for basie radicals (C) Confirmatory tests for acid radicals Calssification of Basic Radicals The qualitative analysis of basic radicals i based on the concept of solubility product, solubility and common ions. These conepets play very important role even in the classification of radicals in six groups and their group reagents.The common occuring cations have been divided into six groups. Group | Group reagent Basic radical | Composition and colour of the ppt. | DiL Her ag ‘AgCI...... White Pb PbCI:...... White He White ILA | HS in the presence | Hg™ HigS...... Black of dil. HCL Black Bi BipSs......Black cu CuS.....-Black ca CdS...... Yellow FS in the presence | As ‘AsiSs......Yellow 1B | ofdil. HCI Sn\ SnS2......Yellow Sb SbySs......Orange Sn? SnS...... Brown Wi | NH,OH in the Fe" Fe(OH)....... Reddish brown presence of excess of NHAC Cr(OH)s......Dirty green AI(OH)....-. White gelatinous ppt TV. | HGS in presence of CoS......Black NH,OH Nis......Black Zn8.....-Bluis white MnS... Buff (flesh) coloured V.__| (NH):COs in the BaCO3......White presence of NHOH S1C0s......White CaCOs......White VI. [No specific group | Ma™™ Mg(NH.)PO,...... White reagent Nat Zero | NaOH NH; NAG gas is evolved z =1. Ist Group Basic Radicals : (Ag’, Pb, Hg3") Original solution uct White ppt Fiterate [076% Residue | (g"",Ae) Coot [kr Kc, White Yellow Yellow oe ra bi rife residue that disolve 4 HNO, inquest Whiley (Hg,") (Ag) 2. Ind Group Basie Radicals : Original solution or Ist group filtrate Original solution or Ist group filtrate (Uf lst group is absent) Sfaue Filthe Ri Group TIA, up 1B (ug®, Cu”, Ca", Bi”, Po") (As? As®, Sb") (Sb", Sn, Sa") Residue Filtrate (Hg PCa", Bi", Pb") = oo wut Fittrate i pt Bi tit ee aoe cee ary pt ’ i Residue Filtre as vee (White pre) (Cu", Ca) ‘atalhie ten) a Sareea a WT ppt of Black pt RFA, Eccl (BiOCl) (BD Chocolate Yellow ppt. coloured pt ca) Group IB filtrate Yellow Filrate pt oo Ist partsNH.OH par diag mastNO. | sold oxalic acidin excess+H.S | Fe.tetander Orange pet White ppt finaly grey Yeti pot ws rally g : Sb Sn (as) oe cayI1Ird Group Basie Radicals Firat of ind group Peer cea ‘ : ¥ éSidue (Fe") Fitts (AU) Frctrecmy——Ywnisen "Ln Prussian Blood red uci blue(Fe") colour Fe") | ¥ 2 (2) Yellow ppt. White of (PbCrO,) gelatinous (cr) pee (Al) 4. IV Group Baise Radicals : (Ni, Co”, Mn", Zn®*) Filtrate of tlrd group HOHA+ HS pe Resifue (Ni, Co") Filfate Disnlig nia vp Pent yo dynes and add ater NsOH+ Beal, ‘YAO! Sol. beat (KHICO, oc NaHCO) Residue Filtrate Sire war Disbve da Dinctytghoxiney APPICgreen —BICKPOt Pink colour or White ppt. (Zn) ee Cy (8) Violet colour (Mn") catlet red ppt. (Ni") 5. Vth Group Basic Radicals : (Ba*, Sr”, Ca™) IVth group filtrate (0 Heat toronove HS {i NIKON (H.C, White ppt. + (Dissolve in inno minimum ‘quantity of hot CH.COOH + K,Ci0, Sol Filtrate (Sr, Ca”) Yellow ppt. (Ba°) }H(NH,)SO, softer removing Ba) White Spt. (Sr) rilfate Yost. ae removing Be" se) White ppt. (Ca)6. VI Group Basic Radical Filtrate of Vth group any pian Now add NH,OH ti NeJHPO, sketch with gas od White erystalline ppt. 7. Zero Group Basic Radical : It contains NH,® ion. (a) The salt is heated with NaOH, ammonia is evolved. The ammonia gives white fumes with HCl (b) NH} gives brown ppt. with Nessler’s reagent Reactions NH,C1+ NaOH —+ NaCl+ NHy + 11,0 NH, +HCl—>NH,CI NH,Cl4-2K, Hal, +3KOH —» NH,HgOHg1 + 7K1+2H,0 Rea lve PbCl; + KyCrO, —+ PbC10 + 2KCI ‘Yelow ppt PbCr0, + 4NaOH —+ Na,PbO, + NayCrO, +2H,0 Ag AgCl+2NH,OH—+ Ag(NH,)3C1+2H0 Diaminester Dehli ‘Ag(NHy C+ 2HNO, —> AgCl+2NH,NOy Whitey Hg,Cl, +2NH,OH —> Hg + Hg(NH, )C1+ NH,C1+2H,0 ‘Bick He SHCL+ HNO, —>NOCI+2H,0+2¢1 2Hg(NH, )C1+ 6Cl— 2H1gCl, + 4HCL4 Ny Hg +2Cl— gc, SHCI+ HNO; —+2H,0 + NOCI+2C1 3HigS +2NOCI+4C| —3H1gCl; + 2NO+35 Po? PbSO, + 2CH;COONH, —»Pb(CH3COO)>, (NH,):S0,7) Pb(CH,COO); + K Cr, —>PbCrO, +2CH\COOK,Bit Bi(OH); +3HCI—>BiCl; +31 BiCI, +H,O—> BiOCI + 3HCI Wie BiCI, +3NaOH—>Bi(OH),+3NaCl 2Bi(OH), +3Na,Sn0, —> 2Bi (OH); +3H;0 Sadsunnite Bek CuSO, + 4NH,OH—3[Cu(NH), SO, +410 [Cu(NH,),]80, + 4CH,;COOH—>CuSO, + 4CH,COONH, 2CuSO, +K[Fe(CN), —>Cug[Fe(CN)g] 4 42K 80, (Cope fercyatiectelns own} ca [Ca(NH,), }S0, +4KCN—>K,[Cd(CN),]+K,80, +4NHy K,[Ca(CN),]+ HyS—> CaS +2KCN +2HCN vllow rt. ee As;S,+10HNO;——> 2HAsO, — +10NO, +5S+2H,0 Arsenic acd Solub le) HAsO, +12(NH,);MoO,——> _ (NH,);As0,.12Mo0, + 2INH,NO, +12H,0 Yello po armoniumarsenomelydate Ie Fe(OH); + 3HCI—> FeCl, + 3H, Sobble FeCl; +3NH,CNS—+Fe(CNS)+3NH,CI ‘Blooded AFeCls +3K,[Fe(CN)g]—>__FelFe(CN)gs_+12KCL Feneocyanie Prin) NaxCr0,, + Pb(CHjCOO); —>PbC10,+2CH\COONa Yellow pe NaAlO, +NH,CI-+H,0—> Al(OH)s+ NH, + NaCl Whiepota Zn ZnCl; + 2NaOH—>Zn( OH ), + 2NaCl White ppt Zn( OH), + NaOH —>NazZn0> + 2H, (Soluble) NapZnO} + H;S—> ZnS + 2NaOH White ppt MaCl; + 2NaOH——>Mn( OH), + 2NaCl Ma(OH), +O—>Mn0, +H0 2MnO» + 4HINO;——>2Mn( NOs )y +2H0 +02 2Mn( NOs ), +SPbs0, + 26HNO;—>2HMn0, +15Pb(NOs )y +120 Permanganie acid (pink ) Ni* CoC, + 2NaHCO; —>Co( HCO5 ), + 2NaCl Co( HCO; ), + 4NaHCO; —+NayCo(CO5 ), +3H20 +3C02 Br + 20 —>2HBr +0 2NaxCo(CO3 }, + HO +O —>2Na;Co( CO; ), +2NaOH, Sod, cobalt carbonate (Green colouration ) NiCl, + 2NaHCO; —> NiCOs +2NaCl + H30 + CO> 2NiCO) +O—>Niz0; +20, (Black) Ba?" (barium) Ba(CI (strontium) (00), + KsCr0, —>BaCi0, + 2CH;COOK St( CHsCOO ), + (NH, )y SO, —51S0, + 2CHsCOONH, White ppt. (caleium) Ca( CHsCOO), + (NHy ), C:0; —> CaCO, + 2CH;COONH, White pptDRY TEST Dry tests are of great importance as these tests give clear indications of the presence of certain radicals, The following tests are performed in dry state: (Flame test (ii) Borax bead test (ii) Miero-cosmie salt bead test (iv) Charcoal cavity test (v)_ Cobalt nitrate charcoal test Flame Test ‘Alkali and Alkaline earth Metals Salts give characteristic colour when introduced in Bunsen flame. The colour produced by them are given below. Li Grimsonred. = Ca_—_— Brick red. Na Goldenyellow Sr Crimson K Violet Ba Applegreen Note Flame test should not be performed in the presence of As, Sb, Bi, Sn and Pb as these radicals form alloy with platinum and hence, the wire is spoiled. Borax bead test (On heating borax the colourless glassy bead formed consists of sodium metaborate and boric anhydride. Na;B407K.10H;0—*“" 5 Na,B,O; "= 5 2NaBO, + B;03 ‘Ghay bond On heating with a coloured salt, the glassy bead forms a coloured metaborate in oxidising flame. CuSO, —>Cu0 + $05 CuO +B;0; —>Cu( BO; ), Copper metaborate (Blue) Colour of the bead in Metal Onidisin Reducing-flame Hot Hot Cold Copper Green Blue Colourless Brown-red Iron Brown-yellow | Pale-yellow | Bottle green _| Bottle green Chromium | Green Green Green Green Cobalt Blue Blue Blue Blue Manganese | Violet Amethyst red | Grey Grey Nickel Violet Brown Gre GreMicrocosmic salt bead test This testis similar to borax bead test. When microcosmic sat is heated, a colourless transparent bead of sodium metaphosphate is formed. Na( NHq HPO, —>NaPOs + NH +10 Sodium metaphosphate Sodium metaphosphate combines with metallic oxides to form orthophosphates which are usually coloured. The shade of the colour gives a clue regarding the presence of metal. Colour of the bead in Metal Oxidising-flame Reducing-flame Hot Cold Hot Cold Copper Green Blue Colourless| Red Iron Yellow or Yellow Yellow Colourless, reddish-brown Chromium | Green Green Green Green Manganese | Violet Violet Colourless, Colourless: Cobalt Blue Blue Blue Blue Nickel Brown Brown Gre ‘Test for acid radicals : Add dil. HCl or H,SO, to a small amount of substanceand warm gently, observe. Carbonate or CO?” a Brisk effervescences of colourless gas CO,; may be carbonate. CaCO, + H,50, —_ C280, +1,0+ CO, @ The gas tums lime water milky CO, + Ca(OH); —+CaCO, + +H,0 iky Gi) Excess of passage of gas through lime water is milkyness disappears CaCO5 +CO) + H{0—+ Ca(HCO} (Soluble) Sulphite or S02 ( Colourless gas with suffocating odour of burning sulphur; may be sulphte. Ca$0, +H,80, —+CaS0, + ,0 +80, t (i) The gas turns orange colour of acidic K,Cr,0, to green KC 0;+H,S0, +380 —>K,S0, +Cry(SO4)3+H30 Orange ‘Gre Note : CO, does not turns orange colour of acidic K,Cr,0, to green Sulphide (s*-) (@ ‘The sulphide salts from H,S which smells lke rotten eggs. NaS H,S0, —»Na,S0, +H,S7ii) On exposure to this gas, the lead acetate paper turns black due to the formationof lead sulphide, Pb(CHyCOO), +HjS—>_ PbS +2CH,COOH ck ot (ii) The sulphides also turn sodium nitroprusside solution violet (use sodium carbonate extract for this rest) NayS+ Nay[FeNO(CN)s]—> PbS, +2CH,COOH Note: Sulphide of lead, calcium, nickel, cobalt antimony and stannic are not decomposed with dil. H,SO,. Conc. HCI should be used for their test. However, brisk evolution of H2S takes place even by use of dil. H2SO4 iffa pinch of zine dust is added. Zn-+H)80, —> ZnSO, +2H HgS +2H Hz + HS Acetate (CH,COO >) (i) Acetates decompose to give acetic acid vapours having characteristic smell of vinegar. 2CHsCOONa + H,S0, —+2CH,COOH + Na,SO, Gi) All acetates are soluble in water and their aqueous solution on addition to neutral FeCl, solution develops a blood red colour due to the formation of ferrie acetate. FeCl; + 3CH;COONa—>(CHjCOO); Fe + 3NaCl Note: 1, The ferric chloride solution supplied in the laboratory is always acidic duc to hydrolysis. It is made neutrla by the addition of dl. solution of NH,OH drop by drop with constant stirring til the precipitate formed does not dissolve. The filtrate is called neutral ferric chloride solution. Before testing acetate inthe aqueous solution by FeCl, it mast be made sure that the solution does not contain, ( co¥ (i) soe Gi) POS Or since these also combine will Fe", Therefore the test of acetate should be performed by neutral ferric chloride solution only after the removal ofthese ions by AgNO, solution, Chloride (CI) )Colourless pungent fumes of hydrogen chloride ae evolved. NaCl + H,$0,—> NallSO, + HCI Gi) The gas evolved forms white fumes of ammonium chloride with NH,OH. NHOH + HCI—> NH,C1+H,0 Whitefmes (il) The gas evolved o solution of chloride salt forms a curdy precipitate of silver chloride with silver nitrate solution, AgNO; +HCI—>AgClL +HINOs (iv). Yellowish-green chlorine gas with suffocating odour is evolved on addition of MnO, to the above reaction mixture, 2NaCI + MnO, + 3H,S0, —> 2NaHSO, + MnSO, +2H,0 + Cl,Note : The curdy precipitate of AgCI dissolves in ammonium hydroxide forming a complex salt, AgNO, +2NH,OH—> AgCI(NH).C1+2H,0 (v) Chromyl chlorde test : When solid chloride is heated with cone, H,SO, in presence of K,Cr,0,, deep red vapours of chromyl chloride are evolved NaCl+H;S0, —>NalHSO, + HCI K.Cr , + 2H SO, —>2KHSO, +2C10; + H,0 C105 +2HCI—> CrO3Cl,_ +H,0 ‘Chronyiclonse ‘These vapours on passing through NaOH sol chromate . form the yellow solution due to the formation of sodium CrO,Cl, + 4NaOH —> Na;CrO, + 2NaCl+2H,0 Yellow oor The yellow solution neutralized with acetic acid gives a yellow solution due to the formation of sodium chromate, Na3CrO, + Pb(CHsCOO), —»PbCrO,+2CHCOONa Yel pt Note 1. This testis not given by the chloride of mercury, tin, silver lead and antimony. 2. The chromyl chloride test is a always to be performed in a dry test tube otherwise the chromy! chloride ‘vapours will be hydrolysed in the test tube. C10 ,Cl, +20 —+1,Cr0, + 2HC1 3. Bromides and ilodies do not give this test. 2. Bromide (Br) (@ _ Reddish-brown fumes of bromine are formed. NaBr + H,SO, —> NalHSO, + HBr 2HBr + HjSO,—>Br, +2H,0 + SO, (i) More reddish-brown fumes of bromine are evolved when MnO, is added 2NaBr + MnO, +3H,S0, —>2NaHSO, + MnSO, +2H,0+Br, (ii) The aqueous solution of bromide or sodium carbonate extract gives pale yellow precipitate of silver bromide which partly dissolves in excess of NH,OH forming a soluble complex. NaBr+AgNOs—> AgBrd +NaNOs Paley AgBr + 2NH,OH—>Ag(NH,)2 Br +2H,0 3. lodide (1) (0) Violet vapours of iodine are evolved. 2K1-+2H,S0, —>2KHSO, + 2HI 2HI-+H,S0, —>1, +80, +2H,0(ii) Violet vapours with starch produce blue colour. + Starch —+ Bluecolour (ii) More violet vapours are evolved when MnO, is added. 2K1+ MnO, + 3H;80, —>2KHSO, +Mn$O, +2H30+1 4. Nitrate (NO;) (Light brown fumes of nitrogen dioxide are evolved. NaNO, +H,80,—> NallSO, + HNO, 2HNO,; —>2H,0 + 4NO, +05 i) These fumes intensify when copper turnings are added, (Cu +4HNO; —>Cu(NO5); +2NO, +2H,0 (iii) Brown ring test : An aqueous solution of salt containing nitrate is mixed with freshly solution of salt solution and cone. H,SO, is poured in test tube from sides, a brown ring is formed an account of the formation of complex at the junction of two liquids. NaNO, +H,$0, —>NaHSO, + HNO, FeSO, + 2HNO, +3H,80, —>3Fe,(SO,); + 4,0 +2NO i 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 ' [Fe(H,0),]SO,.H,0 + NO—>[Fe(H,0);NO]SO, +2H,0 ! Foro aloe Tronren 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1