D.A.V.
PUBLIC SCHOOL
VASANT KUNJ
CHEMISTRY
SALT ANALYSIS
STEP 4: CATION ANALYSIS
Group testing is done first and then the cation is confirmed.
Group Cations Group reagent Expected result
0 Ammonium Dil. NaOH Ammoniacal smell ( pungent
smell)
1 Ag+, Hg22+, Pb2+ Dil. HCl White ppt
2 Hg2+, Pb2+, Cu2+ H2S in presence of HCl. Black ppt
3 Al3+, Cr3+, Fe3+ NH4Cl + NH4OH Gelatinous white ppt
4 Zn2+, Mn2+, Co2+, H2S in presence of NH4Cl Black (Co/Ni ion)/skin (Mn)
Ni2+ and NH4OH /grayish white ppt (Zn)
5 Ba2+, Ca2+, Sr2+ NH4Cl + NH4OH + (NH4)2CO3 White ppt
6 Mg2+ None. Confirmatory test only which
Confirmatory test only for will give white ppt.
which Add NH4Cl, (NH4)3PO4
(ammonium phosphate) and
excess NH4OH to the original
solution.
For group 5, further testing is done.
Barium A yellow precipitate is formed when K2CrO4 is added to the solution.
(Ba2+)
Strontium A white precipitate is formed when aqueous (NH4)2SO4 is added to the solution.
(Sr2+)
Calcium A white precipitate is formed when aqueous (NH4)2C2O4 (ammonium oxalate) and
(Ca2+) NH4OH are added to the solution.
Confirmatory test:
Cation Confirmatory Test Positive
Observation
Ammonium Add sodium hydroxide to the original solution and treat Formation of a
(NH4+) it with Nessler’s reagent (K2HgI4) yellow or brown
precipitate
Lead (Pb2+) (i) Add potassium iodide (KI) to the original solution Formation of a
(ii) Add potassium chromate (K2CrO4) to the original yellow precipitate
solution (for both the tests)
Copper (Cu2+) In the preliminary test, a black precipitate is obtained A blue coloured
from the addition of dilute HCl and H2S to the original solution is formed
solution. Isolate the black precipitate and add excess
ammonium hydroxide to it
Iron (Fe3+) Add concentrated nitric acid to the original solution A blue precipitate is
and heat it. A brown precipitate will form. Add HCl and formed
potassium ferrocyanide (K4[Fe(CN)6]) to it
Aluminium A gelatinous white precipitate is obtained when NH4Cl A floating, blue layer
(Al3+) and excess NH4OH are added to the original solution. is formed on the
Isolate the precipitate and dissolve it in HCl. Now add surface of the clear
blue litmus and NH4OH to it drop-by-drop solution
Cobalt (Co2+) Add solid NH4Cl and excess NH4OH to the original A yellow precipitate
solution and pass H2S gas through it. Dissolve the is obtained.
resulting blue residue in water and add dilute
CH3COOH and KNO2 to it. Now warm the mixture.
Nickel (Ni2+) Add solid NH4Cl and excess NH4OH to the original A black precipitate is
solution and pass H2S gas through it. Dissolve the formed
resulting yellow residue in water (you will now obtain a
green-coloured solution). Add NaOH and bromine
water to this mixture and boil it.
Manganese To the skin-coloured precipitate obtained in the Formation of a white
(Mn2+) preliminary test, add dilute HCl and boil off the H2S. precipitate that turns
Now add NaOH. brown or black when
bromine water is
added
Zinc (Zn2+) Add NaOH (in excess) to the greyish-white precipitate The white precipitate
obtained in the preliminary test. is dissolved
Barium Flame test: Make a paste of the salt by mixing it with a Ba2+:
(Ba2+), few drops of concentrated hydrochloric acid. Now skim Green-coloured
Strontium off some of the paste with a glass rod and expose it to flame
(Sr2+), and a Bunsen Burner’s flame. Sr2+: Crimson red
Calcium flame
(Ca2+) Ca2+: Brick red flame
Magnesium Add NH4Cl, (NH4)3PO4 (ammonium phosphate) and A white precipitate is
(Mg2+) excess NH4OH to the original solution. obtained.
Chemistry of the tests:
1. Tests for NH4+ ion
(NH4)2SO4 + 2NaOH → Na2SO4 + 2NH3 + 2H2O
NH3 + HCl → NH4Cl ( ammoniacal smell with fumes)
Nessler's reagent test
2K2HgI4 + NH3 + 3KOH → HgO.Hg(NH2 )I + 7KI + 2H2O
(Nessler's reagent) (Basic mercury (II) amido-iodine (Brown precipitate)
2. Tests of Pb2+ ions
Lead is precipitated as lead chloride in the first group.
Potassium iodide test
PbCl2 + 2KI → PbI2 + 2KCl
Potassium chromate test
PbCl2 + K2CrO4 → PbCrO4 + 2KCl
3. Tests of Cu2+ ions
3CuS + 8HNO3 → 3Cu(NO3 ) 2 + 2NO + 3S + 4H2O
S + 2HNO3 → H2SO4 + 2NO
2Cu2++ SO42− +2NH3 +2H2O → Cu(OH)2 .
CuSO4 + 2NH4+ + Cu(OH)2 .CuSO4 + 8NH3 → 2 [Cu(NH3)4 ]SO4 + 2OH– + SO4 2−
Tetraamminecopper (II) sulphate (Deep blue)
4. Test for Aluminium ions (Al3+)
AlCl3 + 3NaOH → Al(OH)3 + 3NaCl
Al(OH)3 + NaOH → NaAlO2 + 2H2O
White gelatinous ppt Sodium meta aluminate
In the second test when blue litmus is added to the solution, a red colouration is
obtained due to the acidic nature of the solution. On addition of NH4OH solution drop by
drop the solution becomes alkaline and aluminium hydroxide is precipitated. Aluminium
hydroxide adsorbs blue colour from the solution and forms insoluble adsorption complex
named ‘lake’. Thus a blue mass floating in the colourless solution is obtained. The test is
therefore called lake test.
5. Test for ferric ions (Fe3+ )
Fe(OH)3 + 3HCl → FeCl3 + 3H2O
Potassium ferrocyanide test
4FeCl3 + 3K4[Fe(CN)6 ] → Fe4 [Fe(CN)6]3 + 12KCl
(prussian blue)
Potassium thiocyanate test
Fe3+ + SCN– → [Fe(SCN)]2+ (Blood red colour)
6. Test for zinc ion (Zn2+)
ZnS + 2HCl → ZnCl2 + H2S
ZnCl2 + 2NaOH → Zn(OH)2 + 2NaCl (white ppt of Zn(OH)2)
Zn(OH)2 + 2NaOH → Na2ZnO2 + 2H2O
(excess) Sodium zincate (soluble)
7. Test for Manganese ion (Mn2+)
MnS + 2HCl → MnCl2 + H2S
MnCl2 + 2NaOH → Mn(OH)2 + 2NaCl
(White precipitate)
Mn (OH)2 + [O] → MnO(OH)2 Hydrated manganese dioxide
(Brown colour)
8. Test for Nickel ion (Ni2+)
3NiS + 2HNO3 + 6HCI → 3NiCl2 + 2NO + 3S + 4H2O
( Aqua regia)
9. Test for Cobalt ion (Co2+)
CoS + HNO3 + 3HCl → CoCl2 + NOCl + S + 2H2O
(aqua regia)
CoCl2 + 7KNO2 + 2CH3COOH → K3[Co(NO2)6 ] + 2KCl + 2CH3COOK + NO + H2O
Potassium hexanitritocobaltate(III) (Yellow precipitate)
10. Test for Barium ion (Ba2+)
BaCO3 + 2CH3COOH → (CH3COO)2Ba + H2O + CO2
(CH3COO)2Ba + K2CrO4 → BaCrO4 + 2CH3COOK
Barium chromate (yellow precipitate )
11. Test for Strontium ion (Sr2+ )
SrCO3 + 2CH3COOH → (CH3COO)2 Sr + H2O + CO2
(CH3COO)2 Sr + (NH4)2SO4 → SrSO4 + 2CH3COONH4
Strontium sulphate (White precipitate)
12. Test for Calcium ion (Ca2+)
CaCO3 + 2CH3COOH → (CH3COO)2Ca + H2O + CO2
(CH3COO)2Ca + (NH4)2C2O4 → (COO)2Ca + 2CH3COONH4
Ammonium oxalate Calcium oxalate (White precipitate)
13. Test for Magnesium ion (Mg2+ )
Mg2+ + Na2HPO4 → Mg(NH4)PO4 + NH4OH + 2 Na+ + H2O
Magnesium ammonium phosphate (White precipitate)
