Section I Anions I- Carbonate group Carbonate (CO3--) AND Test Bicarbonate (HCO3-) Carbonate CO3-- Bicarbonate HCO3- Effervescence due to evolution of CO2 gas Effervescence due to evolution of CO2 gas 2- BaCl2 test White ppt on cold (the ppt is soluble in dil HCl) White ppt after boiling (the ppt is soluble in dil HCl) 3- MgSO4 test White ppt on cold White ppt after boiling 4- HgCl2 test Reddish brown ppt No Characteristic Observation 1-dil. HCl 1 II- Sulphur group Sulphide (S--), Thiosulfate (S2O3--) AND Sulphate (SO4--) Test 1-dil HCl test Sulphide S-- Thiosulfate S2O3-- Sulphate SO4-- Rotten egg odor due to evolution of H2S gas Burnt sulphur odor + yellowish white turbidity after worming No ppt from dil solution, if conc solution → white ppt Soluble in dil HCl No reaction white ppt insoluble in dil HCl 2- BaCl2 test No ppt 3- FeCl3 test (sample + few drops of FeCl3) Black ppt Purple color quickly vanishes No reaction 4- lead acetate test Black ppt White ppt soluble in dil HCl White ppt insoluble in dil HCl 5- AgNO3 test Black ppt White ppt → brown White ppt from conc. → black solution (1 drop of the sample + excess AgNO3 ) 6- iodine test 1 mL of iodine solution + few drops of the sample Decolorization of the brown color of I2 + turbidity Decolorization of the brown color of I2 + clear solution Special test for sulphide: sodium nitroprusside test ( sample + 10 % NaOH + few drops of sodium nitroprusside) 2 No reaction purple color Section III III- Halide group Test 1- AgNO3 test 2- lead acetate test Chloride Cl- Iodide I- White cruddy ppt yellow cruddy ppt White ppt. Yellow ppt. Special tests for Iodide: 1- Chlorine water test: ( sample + dil H2SO4 + few drops of chlorine water → shake well → add few drops of chloroform → shake well violet color in the chloroform layer 2- HgCl2 test: HgCl2 + one drop of the sample → scarlet red ppt soluble in excess sample solution. 3- CuSO4 test: Sample + dil H2SO4 + copper sulphate → white ppt in brown solution. 3 Cyanogen group Thiocyanate (SCN-), Ferrocyanide [Fe(CN)6]-4AND Ferricyanide [Fe(CN)6]-3 test Thiocyanate SCN- Ferrocyanide [Fe(CN)6]-4 Ferricyanide [Fe(CN)6]-3 1-AgNO3 test White ppt White ppt Orange red ppt. 2- FeCl3 test (FeCl3 + drop by drop of the sample) Blood red color Prussian blue ppt Brown color 3- FeSO4 test No reaction White ppt. change rapidly into blue ppt. Dark blue ppt. 4- CuSO4 test ( 1 mL sample + drop by drop of CuSO4) Emerald green color Chocolate brown ppt. Green ppt. 5- Co(NO3)2 test 1 mL Co(NO3)2 + 0.5 gm solid Thiocyanate sample → blue color Grayish green ppt. Red ppt. 4 Scheme for Anions 1- Action of dil HCl On cold : * effervescence → CO3-- or HCO3- (differentiation by HgCl2 test) * rotten egg odor → it's S-On hot : * burnt sulphur odor + yellowish white turbidity → it's S2O3-* If no characteristic observation → step (2) 2- Action of FeCl3: 1- blood red color → it's SCN2- dark blue ppt. → it's ferrocyanide 3- Black ppt→ it's S-4- purple color quickly vanishes → it's S2O3-5- reddish brown ppt. → it's CO3-- or HCO3* If no characteristic observation → step (3) 3- Action of BaCl2: * white ppt insoluble in dil HCl → it's SO4-* If no characteristic observation → step (4) 5 4- Action of AgNO3: 1- white ppt. → it's Cl2- Yellowish white ppt. → it's I- 5- Action of HgCl2: Scarlet red ppt. → it's I- 6 Cations The cations are the positively charged part of the salt. The cations are classified into 6 groups. A group is separated from the others by adding a reagent which precipitate the cations of one group and not the others. This reagent is called the "Group Reagent". Group I Group reagent: dil HCl Group precipitate: The cations of group I are precipitated as chlorides. Lead (Pb2+) Test Observation Group reagent: Dil. HCl (1 ml Sample + dil. HCl (drop by drop with strong shaking ) 7 White ppt. Confirmatory tests for Pb2+ 1- Potassium chromate (K2CrO4) test (1 ml sample + 1 ml acetic acid + 1 ml K2CrO4) Yellow ppt. 2- Potassium iodide (KI) test Yellow ppt. 3- Dil. H2SO4 test White ppt. Group II Group reagent: dil. HCl + Na2S Group precipitate: The cations of group II are precipitated as Sulfides. Lead (Pb2+), Copper (Cu2+), Mercuric (Hg2+) AND Cadmium (Cd2+) Pb2+ Cu2+ Hg2+ Cd2+ Black ppt. Black ppt. Yellow ppt. Test Group reagent: Dil. HCl + Na2S (1 ml Sample + 1 ml dil. HCl + 1 ml Na2S) 8 Black ppt. Confirmatory Tests for Pb2+ Test Observation 1- Potassium chromate (K2CrO4) test (1 ml sample + 1 ml acetic acid + 1 ml K2CrO4) Yellow ppt. 2- Potassium iodide (KI) test Yellow ppt. 3- Dil. H2SO4 test White ppt. Confirmatory Tests for Cu2+ Test Observation Emerald green color 1- KSCN Test (2 ml sample + drop by drop of the reagent) 2- Potassium iodide (KI) test (1 ml sample + 1 ml reagent) White ppt. in brown solution Dark blue color 3- Conc. NH4OH test (1 ml sample + 1 ml reagent) Confirmatory Tests for Hg2+ Test Observation 3- Potassium iodide (KI) test (1 ml KI + drop by drop of the sample) Scarlet red ppt. soluble in excess sample 9 Group III Group reagent: NH4Cl + dil. NH4OH Group precipitate: The cations of group III are precipitated as hydroxides. Fe3+ AND Cr3+ Fe3+ Cr3+ Reddish brown ppt. Grayish green ppt. Test Group reagent NH4Cl + dil. NH4OH (Sample + 1 ml NH4Cl + dil. NH4OH then heating) Confirmatory Tests for Fe3+ Test Observation 1- KSCN Test (1 ml sample + 1 ml reagent) Blood red color 2- potassium ferrocyanide test (1 ml sample + 1 ml reagent) Dark blue ppt. 10 Confirmatory Tests for Cr3+ 2 ml of the sample + 2 ml 30% NaOH + 1 ml H2O2 → Boil → Yellow Solution Divide the yellow solution into 2 portions and perform the following tests: Test Observation 1- Portion I + 1 ml acetic acid + 1 ml lead acetate Yellow ppt. 2- Portion II + 1 ml acetic acid + 1 ml BaCl2 Yellow ppt. 11 Group IV Group reagent: NH4Cl + dil. NH4OH + Na2S Group precipitate: The cations of group III are precipitated as sulfides. Co2+ AND Ni2+ Co2+ Ni2+ Black ppt. Black ppt. Test Group reagent NH4Cl + dil. NH4OH + Na2S (Sample + NH4Cl + dil. NH4OH + Na2S then heat) Confirmatory Tests for Co2+ Test Observation 1- potassium ferricyanide test Reddish brown ppt. 2- Vogel's test (Put few crystals of KSCN on a watch glass and add few drops of Co2+ sample) Blue solution 12 Confirmatory Test for Ni2+ Test Observation DMG test: ( 1 ml sample + 1 ml dil NH4OH + drop by drop of DMG) Rose red ppt. 13 Group (V) Group reagent: NH4Cl + dil. NH4OH +NH4(CO3)2 Group precipitate: The cations of group (V) are precipitated as carbonates. Ca2+ and Ba+2 1- Test for Ca2+ Test Observation Group reagent *Sample + NH4Cl + dil. NH4OH then warm , add NH4(CO3)2 and warm again White ppt Confirmatory Tests for Ca2+ 1-Sample + solid NH4Cl + pot. Ferrocyanide then warm for few minutes Creamy white ppt. 2-sample + solid NH4Cl + dil. NH4OH + ammonium oxalate then warm 14 White ppt. 2- Test for Ba+2 Test Observation Group reagent *Sample + NH4Cl + dil. NH4OH then warm , add NH4(CO3)2 and warm again White ppt Confirmatory Tests for Ba+2 Yellow ppt 1- sample + glacial acetic acid + potassium Chromate 2-Sample + solid NH4Cl + pot. Ferrocyanide then warm for few minutes No Creamy white ppt. 3-sample + solid NH4Cl + dil. NH4OH + ammonium oxalate then warm No White ppt. 15 Group (VI) * This group does't have a common reagent that can precipitate all of its cations, so each cation will be tested individually. Mg2+ AND NH4 1- Test for NH4+ Test + Observation Solid Na2CO3 test (put few amount of Na2CO3 powder on a watch glass then add the sample solution and triturate well) Ammonia odor Best Wishes Staff Members of Analytical Chemistry Department 16 A nalysis of unknow n Physical characters : Color :… … … … … … ... odor :… … … … … … Chem ical analysis : Test observation Result Conclusion: the sam ple is… … … … … … … … … … … 17
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