Inorganic Qualitative Analysis PDF

Unit-3 INORGANIC QUALITATIVE ANALYSIS General introduction :- main objective of the qualitative analysis is the detection or identification of individual elements or ions entering in to the chemical composition of a substances. The qualitative analysis may be defined as “The branch of anal...

Unit-3 INORGANIC QUALITATIVE ANALYSIS General introduction :- main objective of the qualitative analysis is the detection or identification of individual elements or ions entering in to the chemical composition of a substances. The qualitative analysis may be defined as “The branch of analytical chemistry which deals with identification of number of constituents present in the given unknown sample is called as qualitative analysis.” A variety of methods , chemical, physical and physio-chemical may be used for qualitative analysis. At this stage we are interested in chemical methods. In qualitative analysis by chemical methods the element or ion to be detected is converted in to some new compound having some characteristic properties on the bases of which one can identify the compound Qualitative analysis can be performed by number methods depending on the amount of substances used for the analytical reactions. These are macro, micro, semi -micro and ultra- micro methods Table 3:1 Different methods of qualitative analysis Size of sample Method Approximate Approximate employed volume of sample volume of reagent 0.1 to 5.0 g. Macro 10 ml 1.0to 5.0 ml 10to100 mg. Semi-Micro 1.0 ml 1 to 5 drops 1.0to10 mg. Micro 0.1ml 1drop When substance is less than 1mg, its analysis is performed under the microscope and is known as ultra-micro analysis Theoretical principles:- qualitative analysis is a analytical technique which concerned with the identification of acidic (-ve ion)and basic (+ve ion) part of the inorganic material in the form of a single salt or as a mixture of two or more simple salts. When simple salt or a mixture of two or more simple salts dissolved in water, it split up in to two types of charged particles one carries positive charge called as positive ion or cation or basic radicals while the other carries a negative charge called as negative ion or anion or a acidic radical. The phenomenon of breaking of the salts in to ions in solution is termed as dissociation. For example in silver chloride silver ion is basic radical while chloride ion is acidic radical The aim of elementary qualitative analysis is to identify number of positive and negative ions present in the given inorganic salt or in a mixture for which number of experiments (called as a tests) are carried out. While caring out the tests, we must concern with the study of formation of or disappearance of 1) Colour 2) Odour 3)Gas 4)Precipitate 5) Complex ion formation and etc. The specific solution used to carry out specific test is called as a reagent and the chemical change observed in the test is known as the analytical or chemical reaction Solubility product Sparingly soluble salt:-The salt or electrolyte added in water if it is having negligible solubility in water at room temperature then the salt is called as sparingly soluble salt Examples – PbSO4, BaSO4 AgCl, CuS, FePO4 etc. When small amount of such a salt is added in water and thoroughly shaken then less amount of its part dissolves in water and ionizes, and gives saturated solution of the salt. Some part dissolves but remains unionized while much amount of its part remains undissolved. Two equilibriums exists when a sparingly soluble salt say AB is in contact with its saturated solution. By applying law of mass action to equilibrium II we get [A+] [B-] / [AB] = K---------------------------(I) The undissolved and unionized part AB are in contact with the ionized part.The concentration of unionized molecule must remain constant. Hence [AB] is constant say K’ hence equation (I) becomes [A+] [B-] = K[AB] [A+] [B-] = KK’ = KSP --------------------------------------- (II) Where KSP is another constant known as Solubility product. It may be defined as “In a saturated solution of a sparingly soluble salt or electrolyte the product of ionic concentration is constant at a given constant temperature” The concentration of a substance in its saturated solution is known as its solubility at a given temperature expressed in unit mole per liter i.e.mol dm-3 -5 Example-Solubility of asparingly soluble salt AgCl is1×10 mol dm-3at 298K. Hence its Solubility product will be Ksp = [Ag+] + [Cl-] =(1×10-5) (1×10-5) =1×10-10 Significance or importance of Solubility product:-The values of Solubility product explains the saturated, supersaturated and unsaturated state of solution 1) When ionic product is less than Solubility product ie [A+] [B-] KSP then the solution produced is unsaturated solution  2) When ionic product is grater than Solubility product ie [A+] [B-] KSP then the solution produced is supersaturated solution at this stage of solution precipitation takes place 3) ) When ionic product is equal to the Solubility product ie [A+] [B-] = KSP then the solution produced is saturated solution Common ion effect:- The phenomenon in which degree of dissociation or ionization of an electrolyte is suppressed by addition of another strong electrolyte containing common ion is called as Common ion effect Consider a weak electrolyte AB whose equilibrium ionization reaction is written as By appelying law of mass action , we get mass law equation for ionization constant k. K= [A+] [B-]/[AB] Now if another strong electrolyte containing common ion either A+or B- is added to the solution of AB it will increase the concentration of either A+or B- Common ion in solution by which equilibrium of the reaction push to the left side hence further ionization of the electrolyte AB will be suppressed by which limited A+ or B- ions produces in solution which are enough for the precipitation of particular group cation Thus the degree of ionization of an electrolyte is suppressed by the addition of strong electrolyte containing common ion is known as Common ion effect. Example:-In the precipitation of IInd group radical addition of HCl will suppress the ionization of H2S due to a Common ion effect  Application of Solubility product and Common ion effect in separation of cations into groups :-The common procedure is set for analysis of 24 cations. According to their tendency of precipitate formation with particular group reagent they are divided into six(6) groups It should be noted that When ionic product is grater than Solubility product ie [A+] [B-] KSP then the solution produced is supersaturated solution at this stage of solution precipitation takes place Table 3:2 Separation of cations in to groups Group No. Cations Group reagents Precipitation reaction (one example) I Ag +, Hg2+, Pb2+ Dilute HCl Ag ++HCl→ AgCl ↓+H+ II IIA-Cu2+,Cd2+Hg2+,,Pb2+, Dilute HCl +H2S gas Bi3+. IIB-Sn2+,Sn4+,Sb3+ SB5+ HCl As3+,As5+. Cu2++H2S-→CuS↓+2H+ IIIA Fe3+,Al3+ Cr3+. NH4Cl&NH4OH NH4Cl 3+ Fe +3NH4OH-→ Fe(OH)3↓+3NH4+ IIIB Co2+,Ni2+, Mn2+, Zn2+. NH4Cl+NH4OH& NH4Cl+NH4OH Zn +H2S------→ZnS↓+2H+ 2+ H2S gas IV Ca2+,Ba2+, Sr2+. NH4Cl+NH4OH& Ca2++(NH4)2CO3--- (NH4)2CO3 NH4Cl+NH4OH - ----------→ CaCO +. + 3↓ 2NH4 V Mg2+ NH4Cl+NH4OH& NH4Cl+NH4OH Na2HPO4 2+ Mg +Na2HPO4---------→ MgHPO4↓+2Na+ VI Na+,NH4+,K+ No particular reagent --------- Group I :-Cations:-Ag+,Hg2+, Pb2+ Group reagents :-Dilute HCl Precipitation reaction :-1)Ag++HCl → AgCl + H+ , 2)Hg+++2HCl→HgCl2 +2H+ The AgCl,HgCl2, PbCl2precipitates of Ist group cations are having lowest Solubility product (KSP) value while further group cation halides are having higher KSP values hence halides of Ist group get precipitated while halides of further group cations remains in solution. Group II:- Cations:- Group IIA:-Cu2+,Cd2+Hg2+,,Pb2+,Bi3+. Group IIB:-Sn2+,Sn4+,Sb3+ SB5+ As3+,As5+. Group reagents :- Dilute HCl andH2S gas Precipitation reaction :- HCl 1) Cu2++H2S-→CuS+2H+ HCl 2) Sn2++ H2S→SnS+2H+ The sulphide precipitates of IInd group cations are having lower Solubility product (KSP) value while further group cation sulphides are having higher KSP values hence sulphides of IInd group get precipitated while sulphides of further group cations remains in solution. As sulphide precipitate of IInd group cation are having low Solubility product (KSP) Values, amount of sulphide (S--)ions required for the precipitation of these cations are very less. Hence ionization of H2S is carried out in presence of dilute HCl which gives H+ common ion in solution. Due to common ion effect of H+ ion from HCl the ionization of H2S get suppressed by which limited S--ions will be produced which will be enough for complete precipitation of IInd group cations. Group IIIA :-Cations:- Fe3+,Al3+ Cr3+. Group reagents :- NH4Cl&NH4OH Precipitation reactions:- NH4Cl 1) Fe3++3NH4OH → Fe(OH)3+3NH4+ NH4Cl 2) Al3++3NH4OH → Al(OH)3+3NH4+ The hydroxide precipitates of IIIrd A group cations are having lower Solubility product (KSP) value while further group cation hydroxides are having higher KSP values hence hydroxides of IIIrd group get precipitated while hydroxides of further group cations remains in solution. As hydroxide precipitate of IIIrd A group cation are having low Solubility product (KSP) Values, amount of hydroxide ions required for the precipitation of these cations are very less. Hence ionization of NH4OH is carried out in presence of NH4Cl which gives NH4+ common ion in solution. Due to common ion effect of NH4+ ion from NH4Cl the ionization of NH4OH get suppressed by which limited OH-ions will be produced which will be enough for complete precipitation of IIIrd Agroup cations.  NH4+ (common ion fromNH4Cl suppresses ionization of (NH4OH) NH4OH=========NH4++OH- Group IIIB:- Cations :- Co2+,Ni2+, Mn2+, Zn2+. Group reagents :-NH4Cl + NH4OH & H2S gas Precipitation reactions NH4Cl+NH4OH 1) Zn2++H2S ZnS+2H+ NH4Cl+NH4OH 2) Zn2++H2S ------→ ZnS+2H+ The cations of IIIrd B get precipitated as sulphide in alkaline medium. The Ksp values of sulphides of IIIrdB group cations being relatively high hence amount of sulphide ions required for precipitation of cations are very high. If the precipitation of IIIrdB group is carried out with H2S in presence of NH4Cl and NH4OH the OH- ion from NH4OH combines with H+ ion from H2S and gives undissociated water molecule as As H+ ions are removed from H2S ,free ionization of H2S takes place by which excess H+ ions produces in solution which are enough for complete precipitation of IIIrdB group cations In above solution NH4Cl added suppresses ionization of NH4OH by common ion effect due to which excess OH- ions may not produces by which hydroxide precipitation of further group cations may be avoided Group IV :- Cations :-Ca2+,Ba2+, Sr2+. Group reagents :-NH4OH+NH4Cl and(NH4)2CO3 Precipitation reactions :- NH4Cl+NH4OH 1) Ca2++( NH4)2CO3--- -----------→ Ca CO3 + 2NH4+ NH4Cl+NH4OH 2) Ba2++( NH4)2CO3--- -----------→ Ba CO3 + 2NH4+ The KSP values of carbonate precipitate of IVthgroup cations are low. Hence for the precipitation of of IVth group cation limited CO32-ions are required. If the precipitation of IVth group cations is carried out in presence of NH4OHandNH4Cl , NH4+ common ions of NH4OH suppresses 2- ionization of (NH4)2CO3 by which limited CO3 ions produces which are inough for precipitation of IVth group cations. The NH4Cl added suppresses ionization of NH4OH by common ion effect unless hydroxide precipitation of Vthgroup cation(Mg++)takes place along with IVth group carbonate precipitate. Group V:- Cation :-Mg2+ Group reagents :-NH4Cl + NH4OH and Na2HPO4 Precipitation reaction :- NH4Cl+NH4OH Mg2++ Na2HPO4--→MgHPO4+2Na+ Mg2+gives white precipitate of MgHPO4 with Na2HPO4 in presence of NH4Cl and NH4OH. Here use of NH4Cl prevent hydroxide precipitation of Mg2+ While the buffer (NH4Cl + NH4OH ) provides optimum pH (pH=10)for effective precipitation of Mg2+ as MgHPO4 Group VI:- Cations :-Na+,NH4+,K+ Group Reagents:-There is no specific reagent for this group.These cations gives their water soluble salts with the reagents Cations of this group are detected and confirmed by their individual characteristic tests. Complex formation:-  The addition product or a complex compound in which number of ligands (equal to coordination number of central metal ion) binds with central metal ion by strong coordinate bonding and produces a compound called as addition product or a complex compound. If it bears any charge then it is known as complex ion. It plays an important role in detection separation and confirmation of most of acidic and basic radicals in Inorganic semi-micro qualitative analysis. The formation of complex ion in solution experiences sudden change in colour, sudden change in solubility and dramatic change in chemical properties. Applications of complex formation:-There are several applications of complex formation in qualitative analysis some of them are 1)Separation of IInd group in to IIA and IIB 2)Separation of Cu2+ from Cd2+as a cyano complex 3) Separation of Co2+from Ni2+ 4) Separation of Cl- from Br - and I- 5)Detection of NO2- and NO3- (Brown ring test) 1)Separation of IInd group in to IIA and IIB:- The IIA group or Copper group cations are Cu++,Cd++Hg++,,Pb++,Bi+3. While the IIB Group or Tin group cations are Sn+2,Sn+4,Sb+3 SB+5 As+3,As+5.The mixture containing IIA and IIB group cations dissolved in suitable mineral acid solution or in distilled water and its solution can be prepared Aqueous solution of IIA and IIB group cations treated with dilute HCl and excess of H2S gas. A sulphide precipitate of IIA and IIB group cations produces. HCl HCl Cu2++H2S→CuS↓+2H+, Sn2+ +H2S→SnS↓+2H+ The sulphide precipitate of IIA and IIB group cations treated with yellow ammonium sulphide ((NH4)2Sx) after gentle worming IIB group precipitate dissolves in((NH4)2Sx) while IIA group precipitate remains as it is hence both can be separated from each other by filtration The precipitate of IIB group cations dissolves in ((NH4)2Sx) and gives clear solution of cations by following reactions 1)Sb2S3+3(NH4)2S→2(NH4)3[SbS3] (Ammonium thio antimonite) 2)As2S3+3(NH4)2S→2(NH4)3[AsS3] (Ammonium thio arsinite) 3) Sb2S5+3(NH4)2S→2(NH4)3[SbS4] (Ammonium thio antimonate) 4)As2S5+3(NH4)2S→2(NH4)3[AsS4] (Ammonium thio arsinate) 5)SnS+(NH4)2S2→(NH4)2[SnS3] (Ammonium thio stannate) 6) SnS2+(NH4)2S→(NH4)2 [ SnS3] All these thioantimonite ,thioarsinite, thioantimonate, thioarsenate and thiostannate salts are water soluble salts which gives clear solution of respective cations used for their confirmatory tests 2)Separation of Cu 2+ from Cd 2+:- Both the cations are IIA group or copper group cations Aqueous solution containing Cu2+and Cd2+ cations treated with dilute HCl and excess of H2S gas. A sulphide precipitate CuS and CdS produces as HCl HCl Cu2++H2S→ CuS +2H+ , CdS+ H2S→ CdS +2H+ The sulphide precipitate of Cu2+and Cd2+digested with concentrated Nitric acid (HNO3) and a clear solution of Cu (NO3)2 and Cd(NO3)2 produces by following reactions CuS +2HNO3→Cu(NO3)2 + H2S , CdS +2HNO3→Cd(NO3)2 + H2S When aqueous solution of Cu (NO3)2 and Cd(NO3)2 treated with excess potassium cyanide (KCN) solution Cd2+ ion gives precipitate of cyanide first while Cu2+ion remains in solution because The Cu(NO3)2 react with KCN and gives unstable Cu(CN)2as Cu(NO3)2+2KCN→Cu(CN)2+2KNO3 2Cu(CN)2 → Cu2(CN)2 +(CN)2↑ (cynogen gas) Cu2(CN)2 +6 KCN→2K3[Cu(CN)4] (unstable complex) By applying law of mass action to the above reaction (I)we get Kinst = [Cu+] [CN-] 4 / [Cu(CN)4]-3 =5.00×10-28 When Cd(NO3)2 reacts with excess KCN gives very weak cyano complex Cd(NO3)2+2KCN→Cd(CN)2+2KNO3 Cd(CN)2 +2KCN→K2[Cd(CN)4] By applying law of mass action to the above reaction (II)we get Kinst = [Cd+] [CN-] 4 / [Cu(CN)4]-2 =1.4×10-17 The ionization constant value for [Cd(CN4)]-2is higher than [Cu(CN)4]-3due to which excess Cd++ ions remains free in solution than Cu ++ions Hence free Cd++ Ion from solution precipitated first with H2S gas than Cu++ ions. 3)Separation of Co2+ from Ni 2+:- Both the cations are IIIrdB cations Aqueous solution containing Co2+and Ni2+ cations treated with NH4OH andNH4Cland excess of H2S gas black precipitate of CoS and NiS produces as NH4Cl+NH4OH NH4Cl+NH4OH 1) Co+++H2S------→CoS+2H+ 2)Ni+++H2S------→NiS+2H+ Wash the residue of CoS and NiS with distilled water and treat it with aquargia (HCL+HNO3= 1:3) in a evaporating dish. Evaporate the solution to dryness cool it add littlie distilled water stir well and filter. Clear solution of CoCl2 and NiCl2 produces as 3HCl +HNO3→2H2O+3Cl+NO 1) CoS +2Cl → CoCl2 +S 2) NiS+2Cl → NiCl2 +S Divide the above solution in to two parts and take test for Co2+ and Ni2+ Test for Co2+:-Treate one poartion of above solution with little amyl alcohol , add few crystals of NH4CNS,A shake well. Deep blue coloured alcohol layer produces indicates presence of 2+ Co Co2++4NCS- →[ Co (NCS)4]2- In above test use of water must be avoided because if water is used , pink colored [Co(H2O)6] complex ion produces instead of deep blue or green [ Co (NCS)4]2- complex ion NI2+present in the solution does not form colored complex with NCS- ion. Hence Co2+ is detected in presence of Ni2+ Test for Ni2+:- To another portion of test solution add excess NH4OH till alkaline and enough alcoholic dimethyl glyoxime solution the scarlet red colored precipitate of [Ni(Dmg)2]produces indicates confirmation of Ni2+ Dimethyl glyoxime is specific reagent for Ni2+ it gives scarlet red precipitate for Ni2+ in alkaline medium but it does not gives such a precipitatefor Co2+.  Scarlet red coloured complex of Ni(Dmg)2 Detection and separation of acidic radicles ( byComplex formation) 1)Separation of Cl- from Br –and I-:- All the halides are similar in properties the group reagent for halides is silver nitrate (AgNO 3) which gives halide precipitate as AgCl(white ),AgBr(pale yellow) and AgI (yellow) which all are insoluble in dilute HNO3 MX=AgNO3→AgX↓+MNO3 Where X=Cl-,Br- or I- and M=Na+ or K+ Cl- can be separated from Br- and I- as, the precipitate of AgCl ,AgBr and AgI treated with aqueous ammonium carbonate solution.Silver chloride gives clear solution of amine complex while AgBr and AgI are sparingly soluble in ammonia solution hence remains undissolved the solution is centrifuged.The centrifugate containing Cl- acidified with dilute HNO3.AgCl get reprecipitated as a result of decomposition of ammine complex. Ag++Cl- →AgCl↓ AgCl ↓+(NH4)2CO3 →[Ag(NH3)2]Cl +H2O+CO2 [Ag(NH3)2]Cl+2HNO3 → AgCl↓+2NH4NO3 In this way Cl-ion detected and separated from the mixture containing Cl-, Br- and I-.NH4OH is not used in the above reactions because AgBr is partially soluble in ammonia 2)Detection of aNO2- and NO3-(By Brown ring test) If the given mixture contain both NO2- and NO3- together both can be detected by Brown ring test as follows a)Detection and confirmation of NO2-:-Treat the aqueous solution of a mixture containing NO2- and NO3- with cold, fresh and saturated solution of FeSO4in a clean test tube to it add dilute CH3COOH solution from the side wall of test tube till solution becomes acidic, brown ring of [FeNO]SO4 complex(or brown coloured solution) produces at the junction of liqude layers indicate conformation of NO2- ion.The brown ring of [FeNO]SO4 produces by following reactions NO2-+CH3COOH → CH3COO-+HNO2 3HNO2 → H2O+HNO3+2NO↑ Fe2++SO42-+NO→ [FeNO]SO4 For detection of NO2- the aqueous solution used must be free from Br- and I- which gives colored complexes with Fe2+. b)Detection and conformation of NO3-:-Treat the aqueous solution of mixture containing NO3- ion (free from NO2- Br- and I-) with enough concentrated H2SO4 shake well cool under tap water. To it add cold, fresh and saturated FeSO4 solution from the side wall of test tube.Brown ring at the junction of two liquid layers indicates the conformation of NO3- ion  The brown ring of [FeNO]2+complex ion produces by following reactions 2NO3-+H2SO4 →2HNO3+SO42- 2HNO3 → H2O+2NO+3[O] 2Fe2++2H++[O] → H2O+2Fe3+ Fe2++NO → [FeNO]2+ The aqueous solution used for confirmation of NO3-must be free from NO2- , Br- and I- ions. Applications of oxidation-reduction:- In qualitative analysis many cation and anaions are detected by means of their behavior towards oxidising or reducing agents 1)Separation of Cl- ,Br –and I-:- The Cl- ,Br –and I- are separated from each other by two probable methods Method –I:-Use of potassium per sulphate (K2S2O8) The oxidation potential of K2 S2O8is very high (2.05V) so used for separation of Cl- ,Br –and I- a)Detection , confirmation and removal of I- :-To the mixture of Cl-, Br– and I- little (K2S2O8) is added and mixture is warmed, evolution of violet fumes indicates detection and confirmation of I- in solution. Heat 2KI+K2S2O8→2K2SO4+I2 ↑ Add slight excess K2S2O8 and warm it gently till violet fumes disappears completely (avoid over heating) - I- completely removed. Here per sulphate oxidizes I- to I2 and itself get reduced to SO42- b)Detection , confirmation and removal of Br-:-Take solution from above test free from I- to it add dilute H2SO4and worm the solution gently. Evolution of brown vapors indicates detection and confirmation of Br-.  Heat 2KBr+K2S2O8+2H2SO4→4KHSO4+Br2 ↑ Add slight excess K2S2O8 and heat the solution gently till brown vapors completely removed (avoid over heating). Br- completely removed. Here per sulphate oxidizes Br- to Br2 c) Detection and confirmation of Cl-:- Take solution from above test free from I- and Br- to it add enough AgNO3 white precipitate of AgCl produces which dissolves completely in ammonia and then reprecipitated with dilute HNO3 confirms presence of Cl- ion in solution Cl- +Ag+ →AgCl↓ AgCl +2NH4OH→[Ag(NH3)2]Cl+H2O [Ag(NH3)2]Cl+2HNO3→AgCl↓+2NH4NO3 Method II:- Use of chlorine water:- a) To the aqueous solution of a mixture containing Cl-, Br– and I- add enough chlorine water and chloroform.Shake well the solution and allow to separate two layers. Violet colour to lower organic layer indicate presence of I-in the given solution. Take upper aqueous layer in a test tube to it add excess chlorine water and chloroform shek well repeat the same till violet colour to lower organic layer does not produces. Here I- get removed completely in this test the Cl2 itself under goes reduction and oxidizes I- to iodine this iodine dissolves in organic layer (chloroform ) and gives violet colour to organic layer 2NaI+Cl2→2NaCl+I2 Or [2I-+Cl2→2Cl-+I2] b) To the aqueous layer from above step(free from I-) add enough chlorine water and chloroform.Shake well the solution and allow to separate two layers yellow colour to lower organic layer indicate presence of Br- in the given solution. Take upper aqueous layer to it add excess chlorine water and chloroform shake well repeat the same till yellow colour to lower organic layer does not produces. Here Br- get removed completely  in this test the chlorine it self under goes reduction and oxidizes Br- to Br2 which dissolves in organic layer (chloroform ) and gives yellow colour to organic layer 2NaBr+Cl2→2NaCl+Br2 Or [2Br-+Cl2→2Cl-+Br2] c)The aqueous layer from above step (completely free from I-,Br- and organic layer) or aqueous solution containing Cl- ,Br –and I- used for confirmation of Cl- which can be treated with AgNO3 solution. A white precipitate of AgCl produces. It can be treated with aqueous ammonium carbonate solution.AgCl gives clear solution of amine complex. If the solution is treated with dilute HNO3 Ci-ion get reprecipitated as AgCl. Hence Cl-ion detected and confirmed. Ag++Cl- →AgCl↓ AgCl+(NH4)2CO3 →[Ag(NH3)2]Cl +H2O+CO2 [Ag(NH3)2]Cl+2HNO3 → AgCl↓+2NH4NO3 2)Separation of NO2- and NO3-:- a) Detection of NO2-:-The aqueous solution containing NO-2 and NO-3 acidified with H2SO4and treated with very dilute KMnO4 solution. Decolouration of KMnO4 solution confirms the presence of NO2- here KMnO4 is reduced by HNO2 to MnSO4 where as HNO2is oxidized to HNO3 2KMnO4+3 H2SO4→K2SO4+2MnSO4+3H2O+5(O) 2KNO2 + H2SO4→K2SO4+2HNO2 HNO2+ (O)→HNO3 Nitrate present in the solution does not interferes in the above test. b)Removal of NO2-:-Under specific conditions nitrite can be reduced to nitrogen and separated from nitrate. To the solution containingNO2- an excess of solid NH4Cl is added and the solution is boiled to expel out NO2- as N2 gas.  Boil NaNO2 +NH4Cl→NH4NO2+NaCl Boil NH4NO2→N2↑+H2O c) Detection of NO3-:-After the removal of NO2-, NO3-can be tested by following tests :- 1)Solution is warmed with Cu foil and conc. H2SO4.Brown gas evolves that turns starch iodide paper black indicates confirmation of NO3-. 2NaNO3+ H2SO4→Na2SO4+2HNO3 Cu+ 4HNO3→ Cu(NO3)2+2NO2↑+2H2O 2)Brown ring test:-[Please refer the brown ring test for NO3-] Spot tests Scientist F.Fiegl and his colleges developed a advanced analytical technique in 1918 for detection and confirmation of basic radicals called as Spot tests analysis. The technique is most superior technique than Inorganic semi micro qualitative analysis because of following advantages Advantages 1) Very simple equipments are required. 2)Very less space is required. 3)Less number of labors are required. 4)Very very small quantity of sample and reagents are required. 5)Very fast technique, less time can be consumed. 6)It is more economical. 7) Simple to operate. 8) Pollution free technique. 9)Carried out even at micro level. The spot test analysis is a simple technique for which one or two drops of sample solution of a high purity material is required. One drop of reagent solution is required. The equipments required are filter paper strips or a spot plate, reagent bottles, sample solution containers, dryer and etc. Experimental procedure for spot test analysis :- Take a drop of sample solution on a paper strip, dry it with the dryer apply a drop of a reagent on it , intense colour develops on a paper strip indicates confirmation of the cation. Spot tests also may be carried on spot plate. Requirements:- The basic requirements of spot test analysis are, High purity (A.R. Grade) inorganic salts and reagents, suitable experimental conditions and cleanliness of equipments and working place are required The technique has some limitations like the reagents required for the analysis must be of higher quality, which are costly. The sample solution must be free from quantamination, prepared by using A.R.grade inorganic salts. The organometallic complex formation or chelation reactions which proceids in spot test analysis may not be clearly understood. Table 3:3 Detection of some cations by spot test analysis Test Observation Inference Colour of the spot 1)Rubeanic acid test:-take a a)Olive green Cu2+present drop of original solution(O.S.) on a paper b)Blue Ni2+ present strip +a drop of reagent- expose toNH3 gas c)Brown Co2+present 2)Dimethyl glyoxime test:- take a drop of O.S. on a paper strip+adropof reagent- Scarlet red colour Ni2+ present and confirmed expose toNH3 gas 3)Potassium ferrocyanide test:- take a drop of O.S. on Intence blue colour Fe3+ present and confirmed a spot plate+a drop of reagent  EXERCISE 1.)Select the most correct alternative and rewrite the sentence again. A. If ionic product-----------the solubility product then the state of solution is saturated state a) b) c)= d)≤ B)When ionic product----------- the solubility productprecipitation occurs a) b) c)= d)≤ C)Degree of dissociation of H2S is suppressed by addition of ---------strong electrolyte a)KCl b)HCl c)NH4Cl d)Na2CO3 D) The group reagent for Vthgroup is---------- a)H2S b)NH4OH c) (NH4)2CO3 d)Na2HPO4 E) The quantity of sample required for semi-micro qualitative analysis is-------- a) 10to100 mg. b)1to10mg. c)0.1to5.0mg. d)100mgto1gm F) Due to common ion effect weak electrolyte becomes-------- a)more weak b)more strong c) remains as it is d)either weak or strong G) Yellow ammonium sulphate is used for separation of group -------- a) IIIArd to IIIBrd b) IInd A to IInd B c)IVth to Vth d) Ist to II nd H) H2S in presence of HCl is a group reagent for  a) IIIArd b) IIIBrd c)IInd d) Vth I) In-------group there is only one Mg2+basic radical a) IIIArd b) IIIBrd c)IInd d) Vth J) the chemical composition of brown ring produced in the test of NO2 is------- a)[FeNO]SO4 b) )[FeNO]Cl2 c)[FeSO4]NO2 d) )[FeCl2]NO K)The spot test analysis technique was developed by scientist-------and his coworkers a) C. V. Raman b) A.I.Vogel c) F.iegl d) P.Waage L)---------gives blood red colouration to ferric ion a)K3 [Fe(CN)6 ] b) K4 [Fe(CN)6 ] c)NH4CNS d) (NH4)2 [Hg(SCN)4] M)Dimethyl glyoxime is a specific reagent for----------- a)Ni2+ b)Co2+ c)Cu2+ d) Fe3+ N) IInd A group cations are called as---------- group cations a)tin b)cadmium c)arsenic d)Copper O)The basic radicals are classified in to different groups according to their tendency to give------ ---with specific group reagent a)precipitate b)complex ion c)double salt d)clear solution P)-------group basic radicals are not having specific group reagent a) Vth b) IVth c)VIth d)IInd ANSWERS:-A-c, B-a, C-b, D-d, E-a, F-a, G-b, H-c, I-d, J-a, K-c, L-c, M-a, N-d, O-a,P-c 2.Write precise note on the following. i)Solubility product ii)Common ion effect iii)complex formation vi)Separation of Cu2+and Cd2+ vii) Separation of Co2+and Ni2+ viii)Separation of NO2- and NO3-.ix)Separation of Cl- from Br –and I- X) Separation of Cl- , Br –and I-by oxidation and reducrion xi) Brown ring test for NO2- and NO3- 3.Discuss the basic principles involved in the semi-micro qualitative analysis. 4.How Cu2+ is separated from Cd2+ by complex ion formation ? 5. How Cl- is separated from Br –and I-by complex ion formation? 6.How NO2- and NO3- are detected by complex formation? 7.Explain in brief separation of of Cl- , Br –and I-by oxidation and reducrion. 8.Explain in brief application of Solubility product and Common ion effect in the separation of IInd group cations. 9. Explain in brie application of Solubility product and Common ion effect in the separation of IIIrd group cations. 10. How Co2+ is separated from Ni2+ by complex ion formation? 11.Explain the role of oxidation and reducrion in the separation of NO2- and NO3-..