INORGANIC CHEMISTRY | TARGET IIT JEE 2014 xl QUALITATIVE ANALYSIS BANSAL CLASSES PARMEV7AGid E-anls is MelGTaEeD) Ideal for Scholars ‘A-10, "GAURAV TOWER’, Road No.-1, |P.LA., Kota-324005 (Raj) INDIA Tel: 0744-2423738, 2423739, 2421097, 2424087 Fax: 0744-2436779 E-mail: admin@bansal.ac.in Website: www.bansal.ac.inIntroduction : Qualitative analysis involves the detection of cation(s) and anion(s) of a salt or a mixture of salts. The systematic procedure for qualitative analysis of an inorganic salt involves the following steps: (a) Preliminary tests +” Physical appearance (colour and smell). Dry heating test. Charcoal cavity test. Charcoal cavity and cobalt nitrate test. Flame test. Borax bead test. Dilute sulphuric acid test. Potassium permanganate test. Concentrated sulphuric acid test. ‘* Tests for sulphate, phosphate and borate. (b) Wet tests for acid radicals. (0) Wet tests (group analysis) for basic radicals, 1. Physical Examination of the Mixture : ‘The physical examination of the unknown mixture involves the study of colour, smell and density. Table : 1 Physical Examination [Experiment —_—«|_ Observations Inference (a) Colour Blue or Bluish green Cu” or Ni* Greenish Nit Light green Fe* Dark brown Fee _ Pink, violet Co” Light pink, flesh colour or dull earthy colour Mn? ‘Shows the absence of White Cu, Ni*, Fe, Fe ia Mn?Co_ ot (b) Smell I Take a pinch of the salt between | _Ammonical smell NEG your fingers and rub with a drop | Vinegar like smell CH;COO | of water Smell like that of rotten eggs | S™ | (©) Density (i) Heavy Salt of Pb or Ba® i) Light flufly powder @ Deliquescence Salt absorbs moisture and becomes paste like (ii) If colourless, may be} Zn(NO}; Chlorides of | | [GBANSAL CLASSES Qualitative Analysis Zn2'Mg eff. Page #2Dry Heating Test : This test is performed by heating a small amount of mixture in a dry test tube. Quite valuable information can be generated by carefully performing and noting the observations here. On heating some salts undergo decomposition thus evolving the gases or may undergo characteristic changes in the colour of residue. These observations are tabulated below along with the inference that you draw. ‘Table : 2 = 7 Observation - Inference | 1. Gas evolved (a) Colourless and odourless gas CO, gas - turns lime water milky co,” () Colourless gas with odour (HS gas - Smells like rotten eggs, turns Hydrated $*~ lead acetate paper black. (ii) SO, gas - Characteristic suffocating smell, turns so," acidified potassium dichromate solution or paper green. (ii) HCI gas - Pungent smell, white fumes with ammonia, | CI” white precipitate with silver nitrate solution. (iv) Acetic acid vapours - Characteristic vinegar CH,COO™ like smell (v) NH, gas - Characteristics smell, turns Nessler's NH,” solution brown, | (©) Coloured gases - Pungent smell (NO, gas - Reddish brown, tums ferrous sulphate NO, or NO, solution black. (ii) Cl, gas - Greenish yellow, turns starch iodide cr paper blue. (iii) Br, vapours - Reddish brown, turns starch paper Br orange red. (iv) I, vapours - Dark violet, turns starch paper blue. r 2. Sublime formed (a) White sublimate NH,’ (b) Black sublimate accompanied by violet vapours. Tr 3. Fusion Themixture fuses. Alkali metal salts or salt containing water of crystallisation, 4. Swelling Themixture swells up into voluminous mass. 5. Residue (Yellow when hot, white when cold. zn" (i) Brown whenhot and yellow when cold. Pb (iii) Original salt blue becomes white on heating Hydrated CuSO4 indicated (iv) Coloured salt becomes brown or black on heating, Co”, Fe™, Fe™, cr, Cu" Ni”, | Mn’” indicated. @ BANSAL GLASSES Qualitative Analysis Page #3Note: + Usea perfectly dry test-tube for performing this test. While drying a test-tube, keeps it in slanting position with its mouth slightly downwards so that the drops of water which condense on the upper cooler parts, do not fall back on the hot bottom, as this may break the tube. + _ Fortesting a gas, a filter paper strip dipped in the appropriate reagent is brought near the mouth, of the test tube or alternatively the reagent is taken in a gas-detector and the gas is passed through it, Gas detector PY) Filter paper ‘strip soaked with reagent Substai Figure : Detection of gas evolved * Do not heat the tube strongly at one point as it may break. Charcoal Cavity Test : This test is based on the fact that metallic carbonate when heated in a charcoal cavity decompose to give corresponding oxides. The oxides appear as coloured incrustation or residue in the cavity. Incertain cases, the oxides formed partially undergo reduction to the metallic state producing metallic beads or scales. Example : (a) ZnSO, +Na,CO, —+ ZnCO, + Naso, ZnCO, ——+ Zn0 (Yellow when hot, white when cold) + CO, (b) CuSO, +Na,CO, —+ CuCO, +Na,SO, cuco, —+ cuo +co,t CuO +C —+ Cu (Reddish scales) + CO t Table: 3 Observation Inference Incrustation or Residue Metallic bead |_ Yellow when hot, white when cold None Zn’ Brown when hot, yellow when cold | Grey bead which Pb marks the paper No characteristic residue Red beads or scales cu" |White residue which glows on heating None Ba’, Ca”, Mg” Black None Nothing definite-generally coloured salt . (G)BANSAL CLASSES Quatitative Analysis Page #4"Cobalt Nitrate Test : In case the residue is white in colour after charcoal cavity test, add a drop of cobalt nitrate in the charcoal cavity. A drop of water is then added and the mass is heated in an oxidising flame using blow pipe. It is cooled and one or two drops of cobalt nitrate solution is added and then again heated in the oxidising flame. Different metal salts give different coloured mass as given in the table. To illustrate : ZnSO, + Na,CO, —+ ZnCO, +Na,SO, ; ZnCO, —+ Zn0 +0, 2Co(NO,), ——+ 2CoO + 4NO, + 0, ; ZnO + CoO —+ Zn0.CoO (or CoZnO,) (Rinmann’s green) Table: 4 SNo.| — Metal Colour of the mass 1. Zine Green 2. | Aluminium Blue 3. | Magnesium Pink 4. Tin Bluish-green Flame Test The chlorides of the metals are more volatile as compared to other salts and these are prepared in situ by mixing the compounds with a little concentrated hydrochloric acid. On heating in a non- luminous Bunsen flame they are volatilized and impart a characteristic colour to the flame as these absorb energy from the flame and transmit the same as light as characteristic colour. Table: 5 Crimson Red / Carmine Red Lithium Golden yellow Sodium Violet / Lilac Potassium Brick red Caleium Crimson Strontium Apple Green / Yellowish Green Barium Green with a Blue centre / Greenish Blue} __Copper Platinum Paste of the ‘mixture in cone. HC] (A) Dipping the platinum wire (B) Introducing the wire in the paste of salt and HCI in the flame Figure : Flame test Qualitative Analysis Page #5Borax Bead Test : On heating borax forms a colourless glassy bead of NaBO, and B,O,. Na,B,0,-10H,0 —*+ Na,B,0, —4-+ 2NaBO, +B,0, On heating with a coloured salt, the glassy bead forms a coloured metaborate in oxidising flame. For example : in oxidising flame copper salts give blue bead. CuSO, —+ Cu +S0, ; CuO +B,0, —+ Cu(BO,), (blue bead) However, in reducing flame the colours may be different due to different reactions. 2Cu(BO,), + C —+ 2CuBO, +B,0, + CO 2Cu(BO,), + 2c —— 2Cu (brown red/red and opaque bead) +2B,0, + 2CO Table: 6 Metal Colour in oxidising flame Colour in reducing flame When Hot ‘When Cold When Hot | When Cold Copper Green Blue Colourless Brown red Iron Brown yellow | Pale yellow/Yellow | Bottle green | Bottle green Chromium Yellow Green Green Green. Cobalt Blue Blue Blue Blue Manganese | Violet/Amethyst| __Red/Amethyst _|Grey/Colourless|Grey/Colourless Nickel Violet Brown/Reddish brown| Grey Grey ‘* Non luminous flame is called oxidising flame. = Luminous flame is called reducing flame. Borax Bead Hot bead (@) inreducing flame _(b) in oxidising flame _(c) Removing bead from platinum wire Figure : Borax bead test @ Allacid radicals which are in JEE syllabus are colourless and diamagnetic. Hence the colour of the salts is only due to the basic radicals. BANSAL GLASSES * Qualitative Analysis Page #6Table: 7 Solubility Chart Solubility/Exception S.No. Anion 1 co, 2 2 3. s 4. |NO,,NO, 5. CH;COO- 6. a 7. Br 8 r 9. so," 10. Po,” Except carbonates of alkali metals ‘and of ammonium, all other normal carbonatesare insoluble. Only the sulphites of the alkali metals and of ammonium are water soluble. The sulphite of other metals are cither sparingly soluble or insoluble. The acid, normal and polysulphide of alkali metals are soluble in water, The normal sulphides of most other metals are insoluble; those of the alkaline carths are sparingly soluble, but are gradually changed by contact with water into solublehydrogen sulphides. Almost all nitrites and nitrates are soluble in water. AgNO, sparingly soluble. Nitrates of mercury and bismuth give basic salts on treatment with water. These are soluble in dilute nitric acid. Acetates are water soluble except Ag(I) and Hg(Il) acetates which are sparingly soluble. Most chlorides are soluble in water. PbCl; (sparingly soluble in cold but readily soluble in boiling water), Hg,Cl,, AgCl, CuCl, BiOCI, SbOCI and Hg, OCI, are insoluble in water. Silver, mercury(I) and copper(1) bromides are insoluble. Lead bromide is sparingly soluble in cold but more soluble in boiling water. All other bromides are soluble in water. Silver, mercury(I), mercury(I), copper(I), lead and bismuth(III) iodides are the least solubie salts. All other iodides are water soluble. The sulphates of barium, strontium and lead are insoluble in water, those of| calcium and mercury(Il) are slightly soluble. Some basic sulphates of| mercury, bismuth and chromium are also insoluble, but these dissolves in dilute hydrochloric or nitric acid. The phosphate of the alkali metals, with the exception of lithium and ammonium, are soluble in water; the primary phosphate of the alkaline earth metals are soluble. All the phosphates of the other metals and also the secondary and tertiary phosphate of the alkaline earth metals are sparingly soluble or insoluble in water. Analysis of Anions (Acidie Radicals) : Analysis of anions (acidic radicals) can be broadly divided in to two groups. (A) Group ‘A’ Radicals : It involves those anions which are characterised by volatile products by reaction with HCV/H,SO, it is further subdivided into two groups as given below. (a) Dilute Sulphuric acid / Diluted Hydrochloric acid : The anions of this group liberate gases oracid vapours with dilute sulphuric acid/hydrochloric acid, BANSAL GLASSES Quatitative Analysis Page #7Table : 8 Inference Observation Gas Radical Effervescence with the evolution of a colourless and | co, co, odourless gas which turns lime water milky. , Evolution of colourless gas having smell of rotten egg which turns lead acetate paper black. HS Colourless_gas having suffocating odour (like s burning sulphur) which tums acidified K,Cr,0, | SO, $0, paper green. Evolution of reddish brown pungent smelling gas which turns : Ne NO, (i) FeSO, solution brownish-blackand 2 a (ii) wet starch-iodide paper blue. HAc(g) CH,COO” Colourless gas having smell of vinegar, * No peculliar gas is evolved. — | Allabove are absent with conc. H,SO,. Table : 9 (b) Concentrated Sulphuric acid group : The anions of this group liberate acid vapours or gases Inference Observation Gas Radical Colourless gas with pungent smell which gives dense white fumes with a glass rod dipped in NH,OH. Reddish brown gas with pungent smell, intensity of reddish brown fumes increases on addition of'a pinch of solid MnO, Alsoit turns starch paper orange red. Evolution of violet vapours which turns starch paper blue, Evolution of reddish brown fumes which intensifies onaddition of copper turnings orbits of filter paper. Starch iodide paper develops a blue-black spot due to the formation of aI,-starch complex. (NO, liberated acts as oxidising agent), HCI Br, NO, a Br NO, ®) Group ‘B? radicals : Anions of this group do not give acid vapours or gases with dilute as well as concentrated H,SO, but are characterised by their specific reactions in solutions. This group is further sub divided into two groups based on the type of the reactions. ion and reduction in solutions : CrO,*, Cr,0,-? ete. itation reactions : These are given by SO,*, PO, ete. BANSAL CLASSES Qualitative Analysis Page #8 SeTable: 10 Observation Inference | WE.orSE.+BaCl(aq) indil. HCland HNO, WEE. or S.E. + cone. HNO, (1-2 mL) + ammonium molybdate and boil > Canary yellow precipitate White precipitate insoluble 507 yi x PO, © — WE. = Water extract. (Salt is dissolved in distilled water) @ — $.E. = Sodium carbonate extract Preparation of sodium carbonate extract : Take 1-2 g of sal/salts mixture and three times the amount of pure solid sodium carbonate in a borosil conical flask.Add 20 mL of distilled water and boil the contents for 10 minutes. Cool the solution, and then filter. The Filtrate is termed as “Sodium carbonate extract”. Sodium carbonate extract is used when (2) saltis only partially soluble in water or insoluble (b) cations interfere with the tests for acid radicals or the coloured salt solutions may be too intense in colour that the test results are not too clear. = _Assodium carbonate extract contains excess of sodium carbonate, it should be neutralised with a sutiable acid before proceeding for analysis of an anion. Mixture of salt, 'Na,CO; and water Figure : Preparation of sodium carbonate extract INDIVIDUAL TESTS (A) Group ‘A? Radicals (a) Dilute sulphuric acid / 1. Carbonate ion (CO,*) ‘* Dilute H,SO, test : A colourless odourless gas is evolved with brisk effervescence. CaCO, + H,SO, —+ CaSO, + H,0 + CO, T * Lime water/Baryta water (Ba(OH),) test : The liberated gas can be identified by its property of rendering lime water (or baryta water) turbid. CO, + Ca(OH), ——> CaCO; 1 (milky) + H,0 On prolonged passage of CO, the milkiness disappears. CaCO, + CO, + H,0 ——+ Ca(HCO,), (soluble) —*-+ Caco, 1 +H,0 + CO, © Magnesium sulphate test (for soluble carbonates) : CO,™ (aq) + MgSO, (aq) —> MgCO, + (white) + $02 (aq) ite hydrochloric acid group : Qualitative Analysis Page #9Silver nitrate solution : White precipitate is formed CO, +Ag* —— > Ag,CO, + White precipitate is soluble in HINO, and ammonia. The precipitate becomes yellow or brown upon addition of excess reagent owing to the formation of silver oxide ; the same happens if the mixture is boiled. Ag,CO, —+ Ag04+C0,t Phenolphthalein is tumed pink by soluble carbonates and colourless by soluble hydrogen carbonates. Mercury(II) chloride does not form precipitate with hydrogen carbonate ions, while in a solution of normal carbonate a reddish-brown precipitate of basic mercury(I) carbonate (GHgO.HgCO, = Hg,0,CO,) is formed. CO, + 4Hg* + 3H,O —+ Hg,0,CO, | + 6H" Lime water milky test is also shown by SO, but CO, does not turn the filter paper soaked in acidified K,Cr,O, green. Soluble bicarbonates give white precipitate with MgSO, (aq)/MgCl(aq) only on heating. Mg +2HCO, ——> Mg(HCO,), —4-+ MgCo, | + H,0 + CO, Action of heat Bicarbonates : 2NaHCO, ——+ Na,CO, + H,0 + CO, Carbonates : Except carbonates of Na, K, Rb, Cs ; the Li,CO, and all alkaline earth metals decompose as given below : LiCO, —+ Li,0 + CO, ; MgCO, ——» MgO + CO, ; Ag,CO, —+ 2Ag+CO, Caco, —4-+ Ca0 + CO, 2, SULPHITE ION (SO,*) : Dilute H,SO, test : Decomposition of salt is more rapidly on warming, with the evolution of sulphur dioxide, CaSO, + H,SO, ——> CaSO, + H,0 + So, T SO, has suffocating odour of burning sulphur. Acidified potassium dichromate test : The filter paper dipped in acidified K,Cr,0, turns green, (1,0? + 2H’ + 380, —+ 2Cr* (green) + 380° + H,O Barium chloride/Strontium chloride solution : White precipitate of barium (or strontium) sulphite is obtained. SO? + Ba*/Sr** ——+ BaSO,/SrSO, 4 (white) White precipitate dissolves in dilute HCI, when sulphur dioxide is evolved. BaSO, J + 2H* ——+ Ba" + SO, 1 +H,0 White precipitate (BaSO, ) on standing is slowly oxidised to sulphate which is insoluble in dilute mineral acids. This change is rapidly effected by warming with bromine water, a little concentrated nitric acid or with hydrogen peroxide. 2BaSO, 1 + 0, —+ 2BaSO, 4 BaSO, v+Br, +H,0 —+ 2Bas0, 4 +2Br +H Hence, reddish brown colour of bromine water is decolourised. 3BaSO, + + 2HNO, ——+ 2BaSO, | +2NO T +H,0 BaSO, L+H, ——+ Baso, 4+H,0 These reactions are not given by carbonates (distinction from carbonates). Zine and sulphuric acid test : Hydrogen sulphide gas is evolved. SO,* + 3Zn** + 8H* ——+ H,$ t+ 3Zn™ + 31,0 Quatitativé Analysis Page # 10