Handout for Qualitative Analysis: Cations Group 1 (Insoluble Chlorides) - Ag+, Pb2+ and Hg22+ Precipitating Reagent: HCl

Ag+:

Chromate can be converted into dichromate when acid is added, CrO42- + 2H+ Cr2O72- + H2O Hg22+: Remarks: 1. Forms a white precipitate, Hg2Cl2 2. Insoluble in hot water Confirmatory Test: Hg2Cl2 + NH3 HgHgNH2Cl (grey to black)

Remarks: 1. Forms an insoluble precipitate AgCl upon the addition of HCl 2. Insoluble in hot water Confirmatory Test: Ag+ + 2NH3 Ag(NH3)2+ Note: AgCl forms again upon the addition of HNO3 Pb2+: Warning: Mercury is a potent heavy metal poison and can cause the Minamata Disease (neurodegenerative) Group 2 (Acid-Insoluble Sulfides) - Hg2+, Pb2+, Bi3+, As3+, Sb3+,Cd2+, Cu2+, Sn4+ - We will only focus on Pb2+, Cd2+ and Cu2+ Precipitating Reagent: H2S OR Thioacetamide in acid medium Pb2+: Remarks: 1. Forms a black precipitate, PbS Remarks: 1. Soluble in hot water Confirmatory Test: Pb2+ + CrO42- PbCrO4 (yellow precipitate) Pb2+ + SO42- PbSO4

Confirmatory Test: *same with that in Group I

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Cd2+: Remarks: 1. Cd2+forms a sulfide which is the only yellow sulfide, CdS

Group 3 (Base-Insoluble Sulfides) - Al3+, Cr3+, Fe3+, Zn2+, Mn2+, Ni2+, Co2+ Precipitating Reagent: (NH4)2S OR Na2S Thioacetamide in basic solution Al3+: Remarks: 1. It forms an insoluble hydroxide, Al(OH)3 which is a white precipitate

OR

Confirmatory Test: Dissolve CdS in acid then add thioacetamide OR H2S Cd2+ + S2- CdS (yellow precipitate) Cu2+: Remarks: 1. Cu2+ can be identified by its distinctly BLUE colored solutions Confirmatory Test: Cu2+ + 4NH3 Cu(NH3)42+ (blue complex in expt 3) Confirmatory Test: Al(OH)3 + HNO3 + Aluminon (dye) Red Lake

Cr3+: Remarks: 1. Forms an insoluble hydroxide, Cr(OH)3 which is green in color

2Cu2+ + Fe(CN)64- Cu2Fe(CN)6 (brown precipitate)

Confirmatory Test: Cr(OH)3 + H2O2 + NaOH CrO42- (yellow)

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CrO42- can further be identified by the ff reactions: Ba2+ +CrO42- BaCrO4 (yellow precipitate) CrO42- + 2H+ H2O + Cr2O72- (orange) Fe3+: Remarks: 1. Solutions of this ion are yellow-colored 2. Forms an insoluble brown precipitate, Fe(OH)3, a brown precipitate

Zn2+: Remarks: 1. Forms the only white colored sulfide, ZnS Confirmatory Test: 3Zn2+ + 2K+ + 2[Fe(CN)6]4- K2Zn3[Fe(CN)6]2(white precipitate)

Confirmatory Test: Fe3+ + SCN- Fe(SCN)2+ (blood red solution)

Mn2+: Remarks: 1. Solutions of this ion are pinkish in color 2. Forms a peach colored precipitate, MnS

K+ + Fe3+ + Fe(CN)64- (ferrocyanmide) KFe(III)Fe(II)((CN)6 (Prussian Blue)

Confirmatory Test: Mn2+ + NaBiO3 (crystals) MnO4- (purple) Note: The formation of purple permanganate is quickly disappears solution due to

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Co2+: Remarks: 1. Solutions of this ion are rose colored/dark pink Confirmatory Test: Co2+ + KNO2 (crystals) K3Co(NO2)6 (yellow precipitate)

Ba2+: Remarks: 1. Forms a white precipitate BaCO3

Confirmatory Test: Ni2+: Remarks: 1. Solutions of this ion are green in color. 2. Forms a black sulfide, NiS Ba2+ + CrO42- BaCrO4 (yellow precipitate)

CrO42- + 2H+ H2O + Cr2O72- (orange)

Confirmatory Test: C4H8N2O2 (Dimethylglyoxime) + Ni2+ Ni(C4H8N2O2)2 (red precipitate) Ba2+ + SO42- BaSO4 (white precipitate)

Group 4 (Insoluble Carbonates/Phosphates) - Ba2+, Ca2+, Mg2+ Precipitating Agent: Na2CO3, K2CO3, or (NH4)2CO3

Flame Test: Green-colored flame

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Mg2+: Confirmatory Test: Mg2+ + HPO42- + NH3 MgNH4PO4 (white precipitate) Flame Test: White-colored flame

Ca2+: Remarks: 1. Forms a white precipitate, CaCO3

Confirmatory Test: Ca2++ C2O42- (oxalate) CaC2O4 (white precipitate) Group V (Alkali Metal Ions) - Na+, K+, NH4+ Precipitating Reagent: NONE Na+: Flame Test: Yellow-colored flame

Flame Test: Orange-red flame

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K+: Flame Test: Lilac/Purple-colored flame

Nitrates and Acetates all are soluble Sulfates all are soluble except Pb2+, Ba2+, Sr2+, Ca2+ Carbonates, Oxalates, Phosphates all insoluble except Na+, K+ and NH4+ Sulfides, Oxides, and Hydroxides all insoluble except Na+, K+, NH4+, Ba2+, Ca2+, Sr2+ Metal ions that dissolve in excess NaOH due to complex formation: Al(OH)3 Al(OH)4Cr(OH)3 Cr(OH)4Pb(OH)2 Pb(OH)4Zn(OH)2 Zn(OH)4Sn(OH)4 Sn(OH)62-

NH4+: Remarks: 1. Turns red litmus paper into blue due to the presence of NH3 Confirmatory Test: NH4+ + OH- NH3 (gas) + H2O

Metal ions that dissolve in excess NH3 due to complex formation: Ni(NH3)62+ (violet) Cu(NH3)42+ (blue) Zn(NH3)62+ (colorless) Ag(NH3)2+ (colorless) Cd(NH3)42+ (colorless) Anions Anions that react with H2SO4 or HNO3: Anion Product Visible Result 2S H2S (g) Rotten egg smell S2O32Sulfur (s) Colloidal sulfur SO32SO2 (g) Respiratory irritant CO32CO2 (g) Effervescence NO3NO2 (g) Brown gas CH3COOCH3COOH Acetic acid smell CrO42Cr2O72Orange solution

Tips in Identifying a Salt Solution or Solid: General Colors of Ions: Co2+ - rose Cr3+ - violet Cu2+ - blue Fe3+- yellow Mn2+ - pink Ni2+ - green The rest are usually colorless. Flame Test: Na: yellow K: purple Ca: brick red Sr: crimson red Ba: green Cu: bluish-green Solubility in H2O:

Specific Anion Tests: 1. PO43Reagent: Ammonium Molybdate PO43- + 12MoO42- + 24H+ + 3NH4+ (NH4)3PO4.12MoO4 (yellow ppt)

2. CrO42Page 6

Reagent: HNO3/H2SO4 CrO42- (yellow) + 2H+ Cr2O72- (orange) + H2O

6. S2Reagent: HNO3/H2SO4 S2- + 2H+ H2S (g) (rotten egg smell) 3. SO42Reagent: BaCl2 Ba2+ + SO42- BaSO4 (white precipitate) Reagent: Pb(OAc)2 Pb2+ + S2- PbS (black ppt)

4. SO327. S2O32Reagent: H2O2 and BaCl2 SO32- + H2O2 SO42- (then same with SO42-) 5. CO32Reagent: HNO3/H2SO4 S2O32- + 2H+ S(s) + SO2 (g) + H2O

Reagent: HNO3/H2SO4 CO32- + 2H+ CO2 (g) (effervescence) + 2H2O

8. C2O42Reagent: Ca(OH)2 CO32- + Ca(OH)2 CaCO3 (s) (lime water/cloudy) + H2O Reagent: CaCl2 or Ca(NO3)2 Ca2++ C2O42- (oxalate) CaC2O4 (white precipitate)

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9. NO3Reagent: FeSO4 in H2SO4 NO3- + 2Fe2+ + 4H+ NO + 2Fe3+ + 2H2O Fe2+ + NO Fe(NO)2+ (brown ring)

12. BrReagent: MnO4- or Fe3+ (or any oxidizing agent) 2Br- + 2Fe3+ 2Fe2+ + Br2 Add colorless nonpolar solvent: CCl4 or hexane

I-, CrO42-, Br- and SCN- interfere with this test by reaction with the iron species present! 10. OAcReagent: Ethanol CH3CH2OH + CH3COOH CH3COOCH2CH3 + H2O

13. IReagent: Fe(NO3)3 source of Fe3+ (or any oxidizing agent) 2I- + 2Fe3+ 2Fe2+ + I2 Add colorless nonpolar solvent: CCl4 or hexane

14. SCN11. ClReagent: AgNO3 Ag+ + Cl- AgCl (white ppt) Reagent: Fe(NO3)3 source of Fe3+ Fe3+ + SCN- FeSCN2+ (blood red solution)

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15. MnO4Reagent: Na2C2O4 5C2O42-(aq) + 2MnO4-(aq) + 16H+(aq) 2Mn2+(aq) + 10CO2(g) + 8H2O(l)

The solution is decolorized!

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