ANALYSIS OF CATIONS

Analytical Chemistry
Decibel P. Elpa
ANALYSIS OF CATIONS

Classification
General Scheme
 ANALYSIS OF CATIONS
Classification

Classification of Metal Cations into Analytical Groups

Group I Cations form precipitates with dilute HCl
Group II Cations do not react with HCl but form precipitates with H2S in
dilute acid medium
Group III Cations do not react with dilute HCl or H2S in dilute acid medium
but form precipitates with ammonium sulfide in neutral or
ammoniacal medium
Group IV Cations form precipitates with ammonium carbonate in the
presence of ammonium chloride in neutral or slightly acidic medium
Group V Common cations which do not react with reagents of the previous
groups
 ANALYSIS OF CATIONS
General Scheme (solution containing some of the cations of Group I to V)
Chart 1 below shows the separation of the Group I cations Ag+ and Pb2+ from the other cations.

Ag+ Pb2+ As3+ Cu2+ Fe2+ Al3+ Ca2+

Mg2+ Na+ NH4+

HCl Group II, III, IV, V

Group I
AgCl (s) PbCl2 (s) *Pb2+ As3+ Cu2+ Fe2+ Al3+ Ca2+
Mg2+ Na+ NH4+
H2O (hot)
Continue using Chart 2
AgCl (s) Pb2+

NH3 HOAc, K2CrO4

Ag(NH3)2+ PbCrO4 (s)

HNO3 yellow ppt confirms presence of Pb2+ *Pb2+ : PbCl2 is more

AgCl (s)
soluble than AgCl, as a
white ppt confirms presence of Ag+
result some Pb2+ will
also appear in Group II
 ANALYSIS OF CATIONS
General Scheme (solution containing some of the cations of Group I to V)
Chart 2 shows the separation of the Group II cations from the remaining cations of Group III, IV, and V.
Pb2+ As3+ Cu2+ Fe2+ Al3+ Ca2+
Mg2+ Na+ NH4+

H2O HCl
Group II thioacetamide
Group III, IV, and V
PbS (s) CuS (s) Fe2+ Al3+ Ca2+
As2S3 (s) Mg2+ Na+ NH4+
KOH, centrifuge Continue using Chart 3
residue Centrifugate
HCl, HNO3,
PbS (s) CuS (s) AgNO3, NaOAc

H2SO4 ; Centrifuge Ag3AsO4

Precipitate, NH4OAc
K2CrO4 Centrifugate, NH3 reddish-brown ppt confirms presence of AS 3+
PbCrO4(s) Cu(NH3)42+
yellow ppt confirms presence of Pb2+ Royal blue color confirms presence of Cu2+
 ANALYSIS OF CATIONS
General Scheme (solution containing some of the cations of Group I to V)

Fe2+ Al3+ Ca2+

Mg2+ Na+ NH4+
NH3 NH4Cl
Group III thioacetamide
Group IV and V
FeS(s) Al(OH)3(s) Ca2+ Mg2+ Na+ NH4+
KOH, Na2O2 Continue using Chart 4
centrifugate
Centrifuge
residue
NH4OAc Fe(OH)2 (s)
NH3
Aluminon HCl, H2O
NH4CNS
Al(OH)3(s)

Red ppt confirms presence of Al 3+ Fe(SCN63+

Blood red color confirms presence of Fe 3+

 ANALYSIS OF CATIONS
General Scheme (solution containing some of the cations of Group I to V)
Chart 4 shows the separation of the Group IV & V cations

Ca2+ Mg2+ Na+ NH4+ NH4+

KOH
NH3 (g)
NH4Cl ,
(NH4)2CO3 red litmus, H2O

Blue litmus
CaCO3 MgCO3
Na+ K+ NaOAc
HCl Conc NH3 , NaOAc Sodium cobaltinitrite
K2CrO4 p-nitrobenzene azoresorcinol Zinc uranyl acetate
NaOH
NaK2Co(NO2)6
NaZn(UO2)3(Ac)9

CaCrO4 (s) Mg(OH)2 Yellow crystalline ppt Yellow ppt confirms

confirms presence of Na+ presence of K+
White ppt confirms Blue ppt confirms
presence of Ca2+ presence of Mg2+