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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

OR

Al3+:
Remarks:
1. It forms an insoluble hydroxide, Al(OH)3 which is a
white precipitate

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:
Al(OH)3 + HNO3 + Aluminon (dye) Red Lake

Confirmatory Test:
Cu2+ + 4NH3 Cu(NH3)42+ (blue complex in expt 3)

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

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

K+ + Fe3+ + Fe(CN)64- (ferrocyanmide)


KFe(III)Fe(II)((CN)6 (Prussian Blue)

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)

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

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

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Co2+:
Remarks:
1. Solutions of this ion are rose colored/dark pink

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

Confirmatory Test:
Co2+ + KNO2 (crystals) K3Co(NO2)6 (yellow precipitate)

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+

Flame Test: Green-colored flame

Precipitating Agent: Na2CO3, K2CO3, or (NH4)2CO3


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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

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

Solubility in H2O:
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)62Metal 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.

Specific Anion Tests:


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

Flame Test:
Na: yellow
K: purple
Ca: brick red
Sr: crimson red
Ba: green
Cu: bluish-green

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2. CrO42Reagent: HNO3/H2SO4
CrO42- (yellow) + 2H+ Cr2O72- (orange) + H2O

6. S2Reagent: HNO3/H2SO4
S2- + 2H+ H2S (g) (rotten egg smell)
3. SO42-

Reagent: Pb(OAc)2
Pb2+ + S2- PbS (black ppt)

Reagent: BaCl2
Ba2+ + SO42- BaSO4 (white precipitate)

4. SO32-

7. S2O32-

Reagent: H2O2 and BaCl2

Reagent: HNO3/H2SO4

SO32- + H2O2 SO42- (then same with SO42-)

S2O32- + 2H+ S(s) + SO2 (g) + H2O

5. CO32Reagent: HNO3/H2SO4
CO32- + 2H+ CO2 (g) (effervescence) + 2H2O

8. C2O42Reagent: CaCl2 or Ca(NO3)2


Reagent: Ca(OH)2

Ca2++ C2O42- (oxalate) CaC2O4 (white precipitate)

CO32- + Ca(OH)2 CaCO3 (s) (lime water/cloudy) +


H2O
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9. NO3-

12. Br-

Reagent: FeSO4 in H2SO4

Reagent: MnO4- or Fe3+ (or any oxidizing agent)

NO3- + 2Fe2+ + 4H+ NO + 2Fe3+ + 2H2O


Fe2+ + NO Fe(NO)2+ (brown ring)

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. OAc-

13. IReagent: Fe(NO3)3 source of Fe3+ (or any oxidizing


agent)
2I- + 2Fe3+ 2Fe2+ + I2

Reagent: Ethanol
CH3CH2OH + CH3COOH CH3COOCH2CH3 + H2O

Add colorless nonpolar solvent: CCl4 or hexane

14. SCN11. Cl-

Reagent: Fe(NO3)3 source of Fe3+

Reagent: AgNO3

Fe3+ + SCN- FeSCN2+ (blood red solution)

Ag+ + Cl- AgCl (white ppt)

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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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