C2710 Qualitative Analysis of Group 2 Metal Ions

Qualitative Analysis of Group 2 (IIA) Metal Ions
The Qualitative Analytical Group IV Ions – The Carbonate Group
Ca2+, Sr2+, Ba2+, (Mg2+)
The Group 2metal ions are precipitated as the white carbonates by aqueous
NH4CO3 in ammonium buffer, pH ≈ 9.2, thus ammonium carbonate is the group
reagent. Aqueous ammonium carbonate solution is essentially a mixture of
equivalent amounts of NH4OH and NH4HCO3, i.e. an ammonium buffer.
NH4+ + CO32- +H2O → HCO3- + NH4OH
Under these conditions, i.e. at pH 9.2, Mg2+ ions will not precipitate, they will
remain in solution, even though magnesium hydroxide,Mg(OH)2 and basic
magnesium carbonate, (MgOH)2CO3are slightly soluble. The hydroxide begins to
precipitate at pH >10.40 and becomes complete at pH 12.42.
The general precipitation reaction is
M2+ + HCO3- + NH4OH → MCO3 + CO2 + NH4+
The carbonates are soluble in mineral acids, except for BaCO3 which does not
dissolve in sulphuric acid, H2SO4, because it dissolves to form the insoluble
barium sulphate, BaSO4, hence no physical change would be observed.
MCO3(s) + H3O+→ M2+(aq) + H2O + CO2(g)
1. Insoluble phosphates
The Group 2 metal ions are precipitated as theinsoluble white phosphates by the
action of disodium hydrogen phosphate, Na2HPO4 or diammonium hydrogen
phosphate, (NH4)2HPO4
M2+(aq) + HPO42(aq)-→ MHPO4(s)
Ba2+(aq) + HPO42(aq) → BaHPO4(s)
If the precipitation reaction in carried out in an alkali medium the hydrogen

phosphate is converted to the neutral salt, the orthophosphate, PO43- is formed
HPO42(aq) + OH- → PO43-(aq) + H2O
3Ba2+(aq) + 2HPO42(aq) + OH-→ Ba3(PO4)2(s)+ H2O

The phosphates dissolve in mineral acids including acetic acid, except for the
phosphates of Ba which are insoluble in sulphuric acid for the same reason above
for the carbonates.
MHPO4(s) + 2H3O+→ M2+ + H3PO4(aq) + 2H2O
e.g. CaHPO4(s) + 2H3O+→ Ca2+ + H3PO4(aq) + 2H2O
The dissolution of the hydrogen phosphate when heated with acetic acid is
accounted for by the formation of the more soluble dihydrogen-phosphate
Ba(H2PO4)2
2MHPO4(s) +2CH3COOH(aq) → M(H2PO4)2 +M(CH3COO)2
e.g. 2BaHPO4(s) + 2CH3COOH(aq) → Ba(H2PO4)2(aq) +Ba(CH3COO)2(aq)
2. Insoluble oxalates
The Group 2 metal ions are precipitated as the insoluble oxalates by the action of
ammonium oxalate, (NH4)2C2O4)2.
M2+(aq) + (NH4)2C2O4)2 → MC2O4(s) + 2NH4+(aq)
Barium oxalate is soluble in HCl, HNO3 and when heated with acetic acid, but
insoluble in H2SO4. Strontium oxalate and calcium oxalate dissolve in mineral
acids, strontium oxalate dissolve when heated with concentrated acetic acid but
calcium oxalate is insoluble in acetic acid soluble in acids including acetic acid
3. Insoluble sulphates
Sulphuric acid and soluble metal sulphates will precipitate the metal ions as the
insoluble white precipitates of the sulphates, MSO4.
Ba2+(aq)+HSO4-(aq)+ H2O→ BaSO4(s)+H3O+(aq)

Ba2+(aq)+SO42-(aq)→ BaSO4(s)
Barium sulphate forms immediately because it is less soluble, the solubility
products constants are:
BaSO4 Ksp = 1.10 x 10-10
SrSO4 Ksp = 3.20 x 10-7

CaSO4 Ksp = 2.37 x 10-5
It implies that CaSO4 is slightly soluble, hence gypsum water (aqueous solution of
CaSO4) will precipitate Ba2+ and Sr2+ ions from solutions and the insoluble
sulphates.
4. Action of potassium chromate
Aqueous potassium chromate solution, K2CrO4 will form a yellow precipitate with
Ba2+ and Sr2+, but not with Ca2+.
M2+(aq) + CrO42-(aq) →MCrO4(s)
Barium chromate is soluble in strong acids, but not in acetic acid, strontium
chromate is also soluble in strong acids as well as in aceticacid.
In the presence of sodium acetate solution, aqueous potassium dichromate

solution, K2Cr2O7 will form a yellow precipitate of barium chromate only with
Ba2+ions but not with and Sr2+and Ca2+. It does not form barium dichromate,
BaCr2O7 as would be expected. An aqueous solution of a dichromate is an
equilibrium mixture of CrO42-, HCrO4- and CrO42- ions.
Equilibrium 1 CrO42(aq)- + H2O → 2HCrO4-(aq)
Equilibrium 2 2HCrO4-(aq) +2H+(aq) + CrO42-(aq)
Overall equilibrium CrO42(aq)- + H2O → 2HCrO4-(aq) + 2H+ + CrO42-(aq)
5. The action of potassium ferrocyanide solution
In ammonium buffermedium of pH 9.2, potassium ferrocyanide (or potassium

hexacyanoferrate (II), K4[Fe(CN)6] forms a white crystalline precipitate with Ca2+
ions. It does not form any precipitate with Sr2+ or Ba2+ ions.
Ca2+(aq) 2NH4+(aq) + [Fe(CN)6]4-(aq) → Ca(NH4)2[Fe(CN)6](s)
6. Flame Test
Barium salts burn ton impart a yellow-green colour to the flame, strontium salts
burn with a characteristic crimson flame colour and calcium salts burn with to
impart a brick-red colour to the flame.
Flow chart for separation of Group 2 (orIIA) metal ions
Aqueous solution containing Mg2+, Ca2+,

Sr2+, Ba2+
Add 6.0M NH4OH until alkaline, then add a few

drops of (NH4)2CO3 let stand for few minutes and filter
Residue Filtrate
CaCO3, SrCO3 and BaCO3 Mg2+
Dissolve in 2.0M HCl and add
a few drops of (NH4)2C2O4
Residue
CaC2O4, SrC2O4, BaC2O4
Dissolve in 2.0M HCl and add

a few drops of K2CrO4
Residue Filtrate
SrCrO4, BaCrO4 Ca2+
Heat with CH3COOH Flame test
and filter
Brick red
flame
Residue Filtrate
BaCrO4 Sr2+
Flame testFlame test
Yellow-green Crimson
flame flame

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Qualitative Analysis of Group 2 (IIA) Metal Ions

The Qualitative Analytical Group IV Ions – The Carbonate Group

Ca2+, Sr2+, Ba2+, (Mg2+)

NH4+ + CO32- +H2O → HCO3- + NH4OH

The general precipitation reaction is

M2+ + HCO3- + NH4OH → MCO3 + CO2 + NH4+

MCO3(s) + H3O+→ M2+(aq) + H2O + CO2(g)

M2+(aq) + HPO42(aq)-→ MHPO4(s)

Ba2+(aq) + HPO42(aq) → BaHPO4(s)

If the precipitation reaction in carried out in an alkali medium the hydrogen

HPO42(aq) + OH- → PO43-(aq) + H2O

3Ba2+(aq) + 2HPO42(aq) + OH-→ Ba3(PO4)2(s)+ H2O

MHPO4(s) + 2H3O+→ M2+ + H3PO4(aq) + 2H2O

e.g. CaHPO4(s) + 2H3O+→ Ca2+ + H3PO4(aq) + 2H2O

2MHPO4(s) +2CH3COOH(aq) → M(H2PO4)2 +M(CH3COO)2

e.g. 2BaHPO4(s) + 2CH3COOH(aq) → Ba(H2PO4)2(aq) +Ba(CH3COO)2(aq)

M2+(aq) + (NH4)2C2O4)2 → MC2O4(s) + 2NH4+(aq)

Ba2+(aq)+HSO4-(aq)+ H2O→ BaSO4(s)+H3O+(aq)

BaSO4 Ksp = 1.10 x 10-10

SrSO4 Ksp = 3.20 x 10-7

4. Action of potassium chromate

M2+(aq) + CrO42-(aq) →MCrO4(s)

In the presence of sodium acetate solution, aqueous potassium dichromate

Equilibrium 1 CrO42(aq)- + H2O → 2HCrO4-(aq)

Equilibrium 2 2HCrO4-(aq) +2H+(aq) + CrO42-(aq)

Overall equilibrium CrO42(aq)- + H2O → 2HCrO4-(aq) + 2H+ + CrO42-(aq)

5. The action of potassium ferrocyanide solution

In ammonium buffermedium of pH 9.2, potassium ferrocyanide (or potassium

Ca2+(aq) 2NH4+(aq) + [Fe(CN)6]4-(aq) → Ca(NH4)2[Fe(CN)6](s)

Aqueous solution containing Mg2+, Ca2+,

Add 6.0M NH4OH until alkaline, then add a few

Dissolve in 2.0M HCl and add

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