Qualitative Analysis
Qualitative Analysis
Qualitative Analysis
MnO, MnO2, FeO, CuO, Co3O4, Ni2O3; sulfides of Ag+, Cu+, Cu2+, Fe2+, Co2+, Pb2+, Hg2+ Black Hydrated Cu2+ salts HgO, HgI2, Pb3O4 Cr3+, Cr6+, Ni2+, hydrated Fe2+ salts Hydrated Mn2+ salts KO2, K2Cr2O7, Sb2S3, ferricyanides Hydrated Co2+ salts Chromates, AgBr, As2S3, AgI, PbI2, CdS CdO, Fe2O3, PbO2, CuCrO4 Blue Red Green Light Pink Orange Reddish Pink Yellow Dark brown
Detecting cations
According to their properties, cations are usually classified into six groups.[1] Each group has a common reagent which can be used to separate them from the solution. To obtain meaningful results, the separation must be done in the sequence specified below, as some ions of an earlier group may also react with the reagent of a later group, causing ambiguity as to which ions are present.this happens because cationic analysis is based on the solubility products of the ions.As the cation gains its optimum concentration needed for precipitation it precipitates and hence allowing us to detect it. The division and precise details of separating into groups vary slightly from one source to another; given below is one of the commonly used schemes.
Qualitative inorganic analysis samples a violet colour. PbCl2 is far more soluble than the chlorides of the other two ions, especially in hot water. Therefore, HCl in concentrations which completely precipitate Hg and Ag+ may not be sufficient to do the same to Pb2+. Higher concentrations of Cl cannot be used for the aforementioned reasons. Thus, a filtrate obtained after first 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 sulfide. For this reason, Pb2+ is usually also included in the 2nd analytical group. This group can be determined by adding the salt in water and then adding dilute hydrochloric acid. A white precipitate is formed, to which ammonium hydroxide is then added. If the precipitate is insoluble, then Pb2+ is present; if the precipitate is soluble, then Ag+ is present, and if the white precipitate turns black, then Hg is present. Confirmation test for lead: Pb2+ + 2 KI PbI2 + 2 K+ Pb2+ + K2CrO4 PbCrO4 + 2 K+ Confirmation test for Silver: Ag+ + KI AgI + K+ 2Ag+ + K2CrO4 Ag2CrO4 + 2 K+ Confirmation test for dimeric mercury ion: Hg 2 Hg + 2 KI Hg2I2 + 2 K+ + 2 NaOH 2 Hg2O + 2 Na+ + H2O
The reagent used can be any substance that gives S2 ions in such solutions; most commonly used are H2S (at 0.2-0.3 M), AKT (at 0.3-0.6 M). The test with the sulfide ion must be conducted in the presence of dilute HCl. Its purpose is to keep the sulfide ion concentration at a required minimum, so as to allow the precipitation of 2nd group cations alone. If dilute acid is not used, the early precipitation of 4th group cations (if present in solution) may occur, thus leading to misleading results. Acids beside HCl are rarely used. Sulfuric acid may lead to the precipitation of the 4th group cations, whereas nitric acid oxidises the sulfide ion in the reagent, forming colloidal sulfur. The precipitates of these cations are almost indistinguishable, except for CdS, which is yellow. All the precipitates, except for HgS, are soluble in dilute nitric acid. HgS is soluble only in aqua regia, which can be used to separate it from the rest. The action of ammonia is also useful in differentiating the cations. CuS dissolves in ammonia forming an intense blue solution, whereas CdS dissolves forming a colourless solution. The sulfides of As3+, As5+, Sb3+, Sb5+, Sn2+, Sn4+ are soluble in yellow ammonium sulfide, where they form polysulfide complexes. This group is determined by adding the salt in water and then adding dilute hydrochloric acid followed by hydrogen sulfide. Usually it is done by passing hydrogen sulfide over the test tube for detection of 1st group cations. If it forms a reddish brown or black precipitate then Bi3+, Cu2+, Hg2+ or Pb2+ is present. Otherwise, if it forms a yellow precipitate, then Cd2+ or Sn4+ is present; or if it forms a brown precipitate, then Sn2+ must be present; or if a red orange precipitate is formed, then Sb3+ is present. To distinguish between ions in the black or reddish brown precipitate, it is first boiled in diluted HNO3. If it is insoluble, then Hg2+ is present. If it is soluble, then Cu2+, Hg2+ or Pb2+ may be present; sulfuric acid is then added to the resulting solution. If a white precipitate forms, then Pb2+ may be present; if no precipitate is formed, then a new
Qualitative inorganic analysis solution is made by adding an excess of ammonium hydroxide in the original salt solution. A resulting blue color indicates the presence of Cu2+, and a white precipitate indicates bismuth. Otherwise, if the precipitate is insoluble then Hg2+ is present. To distinguish between ions in the yellow precipitate, an excess of NaOH is added to the original salt solution to form a white precipitate. The test tube is then shaken, and if the white precipitate dissolves, then Sn4+ is present; otherwise, Cd2+ is present. Confirmation test for lead: Pb2+ + 2 KI PbI2 + 2 K+ Pb2+ + K2CrO4 PbCrO4 + 2 K+ Confirmation test for copper: 2 Cu2+ + K4[Fe(CN)6] + CH3COOH Cu2[Fe(CN)6] + 4 K+ Cu2+ + 2 NaOH Cu(OH)2 + 2 Na+ Cu(OH)2 CuO + H2O (endothermic) Confirmation test for bismuth: Bi3+ + 3 KI (in excess) BiI3 + 3 K+ BiI3 + KI K[BiI4] Bi3+ + H2O (in excess) BiO+ + 2 H+ Confirmation test for mercury: Hg2+ + 2 KI (in excess) HgI2 + 2 K+ HgI2 + 2 KI K2[HgI4] (red precipitate dissolves) 2 Hg2+ + SnCl2 2 Hg + SnCl4 (white precipitate turns gray)
Detecting anions
1st analytical group of anions
The 1st group of anions consist of CO, HCO, CH3COO, S2, SO, S2O and NO. The reagent for Group 1 anions is dilute hydrochloric acid (HCl) or dilute sulfuric acid (H2SO4). Carbonates give a brisk effervescence with dilute H2SO4 due to the release of CO2, a colorless gas which turns lime water milky due to formation of CaCO3. The milkiness disappears on passing the lime water through an excess of the gas, due to formation of Ca(HCO)3. Acetates give the vinegar-like smell of CH3COOH when treated with dilute H2SO4. A blood red colouration is produced upon addition of yellow FeCl3, due to formation of iron(III) acetate. Sulphides give the rotten egg smell of H2S when treated with dilute H2SO4. The presence of sulfide is confirmed by adding lead(II) acetate paper, which turns black due to the formation of PbS. Sulfides also turn solutions of red sodium nitroprusside purple. Sulphites produce SO2 gas, which smells of burning sulfur, when treated with dilute acid. They turn acidified K2Cr2O7 from orange to green. Nitrites give reddish brown fumes of NO2 when treated with dilute H2SO4. These fumes cause a solution of potassium iodide (KI) and starch to turn blue.
Modern techniques
Qualitative inorganic analysis is now used only as a pedagogical tool. Modern techniques such as atomic absorption spectroscopy and ICP-MS are able to quickly detect the presence and concentrations of elements using a very small amount of sample.
References
[1] E. J. King "Qualitative Analysis and Electrolytic Solutions" 1959, Harcourt, Brace, and World, New York. [2] C. Parameshwara Murthy (2008). University Chemistry, Volume 1. New Age International. p.133. ISBN8122407420.
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