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Qualitative Analysis
I- Group
This group include Ag+, Pb2+, and Hg 22+ . The group reagent is dilute hydrochloric acid. The radicals
are precipitated as their because the solubility product of these chlorides (AgCl, PbCl2 and Hg2Cl2) is
less than the solubility of all other chlorides which thus remain in solution.
Radical Test / observation / Analysis Reaction
Pb+2 Pb+2 ion gives yellow ppt. with PbCl2 + K2CrO4 → PbCrO4(yellow)↓ 2KCl PbCl2
K2CrO4 & KI soln. separately . + 2KI→ PbI2↓(yellow) +2KCl
Hg2+2 Hg2+2 gives black ppt. with NH3 Hg2Cl2+2NH4OH→ Hg(NH2)Cl+
Hg↓+NH4Cl+2H2O
Ag+ (i) AgCl is soluble in NH4OH AgCl+2NH4OH→[Ag(NH3)2]Cl + 2H2O
+
(ii) Ag ion gives yellow ppt. with Ag+ + I-AgI↓(yellow)
KI
Note : PbCl2 is soluble in hot water (but insoluble in cold water) Whereas insoluble in both AgCl &
HgCl2
II- Group
This group includes Hg2+, Pb2+, Bi3+, Cu2+, Cd2+ (all in IIA), As3+, Sb3+, Sn2+ and Sn4+ (all in IIB)
This group reagent in hydrogen sulphide in presence of HCl. These radicals are precipitated as their
sulphieds, whereas the sulphides of other metals remain in solution because of their high solubility
product.
HgS, PbS, Bi2S3 and CuS are black, Cds, As2S3 and SnS2 yellow, SnS brown, and Sb2S3 in orange. The
function of HCl is to decrease ionization of H2S (due to common ion effect) so that only the solubility
product of sulphies of II group radical is exceeded and not that of III, IV and V group. Hence III , IV
and V group radicals are not precipitated by H2S in the presence of HCl.
Pbs and CdS are precipitated only on dilution due to higher Ksp.
IIA and IIB group sulphides are separated by yellow ammonium sulphide (NH4)2Sx in which IIA group
sulphide are insoluble whereas that of IIB are soluble forming thiosalts.

Radical Test / observation / Analysis Reaction

Hg2+2 Adding Hg+2 ion white ppt. 2Hg+2 + SnCl2 → Sn+4 + Hg2Cl2↓ (white)
obtained which turns black HgCl2 + SnCl2 → SnCl4 + 2Hg↓ (black)
Pb+2 + H2SO4 → PbSO4 ↓ (white) + 2H+
Pb+2 (i) In solution, Pb2+ gives white Pb+2 + Cr2O4-2 → PbCrO4↓ (yellow)
ppt, with H2SO4 Pb+2 + 2H- → PbI2↓ (yellow)
(ii) In solution Pb+2 ion gives

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yellow ppt with K2CrO4 & KI
Cu+2 (i) These ion gives dark blue Cu+2 + NH4OH → [Cu(NH3)4]+2 H2O
colour with excess NH4OH (dark blue colour)
+2
(ii) Cu ion gives chocolate 2Cu+2 + K4Fe(CN)6 → Cu2 [Fe(CN)6] ↓ 4k
colour with K4Fe(CN)6 (Chocolate or red brown ppt)
Bi+3 Bi+3 ion gives white ppt, white BiCl3 + H2O → BiOCl ↓ (White) + 2HCl
adding water in HCl soln BiCl3 + 3Na2SnO2 + 6NaOH→
(sodium stanite)
2Bi ↓ + 3Na2SnO3 + 6NaCl + 3H2O
(black sodium stanate)
Cd+2 (i) The yellow precipitate is 3Cds + 8HNO3 →3Cd(NO3)2+
dissolved in 50% HNO3. To the (50%) 4H2O+2NO+3S
resulting solution, NH4OH is Cd(NO3)2+ 2NH4OH→2NH4NO3
added slowly. A white ppt, appears + Cd(OH)2↓ (white ppt)
which dissolve in excess of Cd(OH) + 2NH OH + 2NH NO →
2 4 4 3
NH4OH [Cd(NH3)4] (NO3)2aq + 4H2O
(ii) When H2S gas is passed in this [Cd(NH ) ] (NO ) + H S →
3 4 3 2 2
solution a yellow ppt, appears
CdS ↓(yellow ppt) + 2NH4NO3 + 2NH3

III-Group
This group includes Fe3+, Al3+, and Cr3+. The group reagent NH4OH and in presence of NH4Cl, the
radicals are precipitated as their hydroxides. The function of NH4Cl is to suppress the ionization of
NH4OH so that only the IIIrd group radicals are precipitated, because the solubility product of IIIrd
group hydroxides is less than that IV and VI group hydroxides.
Excess of NH4Cl should be added, or else manganese will be precipitated in III group.
Radical Test / observation / Analysis Reaction
Fe+3, Cr+3 These ion precepts in the form Fe+3 + 3OH- → Fe(OH)3 (red ppt)
& Al+3 of hydroxide on adding NH4Cl Cr+3 + 3OH- → Cr(OH)3 (green ppt)
& NH4OH Al+3 + 3OH- → Al (OH)3 (white ppt)
Note : In the analysis of III group, some drops of cone. HNO3 are also added before oxidizing Fe+2
to Fe+3
Radical Test/Observation/Analysis Reaction
Al3+ White ppt. of Al(OH)3 is soluble in Al(OH)3 + NaOH → NaAlO2 + 2H2O
NaOH (Sodium metaaluminate)

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Cr3+ ppt of Cr(OH)3 is soluble in NaOH + Br2 + H2O → 2HBr + O
Br2 water soln. in this solution when 2Cr(OH)3 + 4NaOH + 3O → 2Na2CrO4 + 5H2O
Na2CrO4 + BaCl2 → BaCrO4 ↓(Yellow ppt) +
BaCl2 is added yellow
2NaCl

Fe3+ (a) Brown ppt of Fe(OH)3 is soluble Fe(OH)3 + 3HCl → FeCl3 + 3H2O
in HCl
(b) When KCNS is added in this
FeCl3 + 3KCNS → Fe(CNS)3 ↓(Blood red) + 3KCl
soln. Blood red colour is obtained
(c) In this soln., on
adding 4FeCl3 + 3K4[Fe(CN)6] →
K4[Fe(CN)6], pussian blue colour is Fe4[Fe(CN)6]3 ↓(Prussian Blue) + 12KCl
obtained

IV-Group
This group includes Co2+, Ni2+, Zn2+, and Mn2+. The group reagent is hydrogen sulphide in ammonical
solution. Radicals are precipitated as sulphides which are insoluble in NH4OH.
CoS, NiS – Black, MnS – Buff, ZnS – White
The function of ammonium hydroxide is to increase the ionization of H2S.
Thus, an excess of sulphide ions will be available and hence the ionic product of IV group sulphides
exceeds their solubility product and precipitates will be obtained.

Radical Test/Observation/Analysis Reaction

Zn2+, Mn2+, These ions in presence of NH4OH MCl2 + H2S → MS ↓ + 2HCl
Co2+, Ni2+ precipitates on passing H2S. CoS,
NiS – Black(soluble in aqua-regia),
MnS – Buff(soluble in HCl), ZnS –
White(soluble in HCl).
Ni2+ In presence of NH4OH, Ni salt on NOH
reaction with dimethyl glyoxime H 3C + NiCl2 + 2NH4OH
CH3
(DMG) turns red ppt. of nickel NOH
dimethyl glyoxime
(C 4H7N2O2)2Ni + 2NH4Cl + 2H2O

Co2+ Cobalt salt turns blue coloration CoCl2 + 4NH4CNS → (NH4)2[Co(CNS)4] + 2NH4Cl
with NH4CNS (blue colour)

Zn2+ In solution, Zn2+ ion turns white ppt. Zn2+ + 2NaOH → Zn(OH)2 ↓(white) + 2Na
with NaOH which is soluble in Zn(OH)2 + 2NaOH → Na2ZnO2 + 2H2O
excess NaOH
Mn2+ (a) Mn2+ ion gives pink ppt with Mn2+ + 2NaOH → Mn(OH)2 ↓(pink) + 2Na

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NaOH Mn(OH)2 + O → MnO2 + H2O

(b) On heating turns black or brown (Black or brown)

V Group
This includes Ba2+, Sr2+ and Ca2+. The group reagent is ammonium carbonate in the presence of NH4Cl
and NH4OH. These are precipitated as carbonates which are insoluble in NH4OH.
The function of ammonium chloride is to suppress the ionization of NH4OH and (NH4)2CO3 and thus
check the precipitation of Mg(OH)2 (along with V group carbonates) because the solubility product of
Mg(OH)2 and MgCO3 is high. Further NH4Cl should also not be added in excess, as the high
concentration of NH4+ ions will decrease the ionization of (NH4)2CO3 to such an extent that sufficient
CO32- ions may not be present and carbonates of this group of metals may not precipitate.
Radical Test/Observation/Analysis Reaction
Ba2+, Sr2+, On adding (NH4)2CO3, these M2+ + (NH4)2CO3 → MCO3 + 2NH4+
Ca2+ precipitates in the form of BaCO3, CaCO3, SrCO3 (white ppt)
carbonates, soluble in CH3COOH
Ba2+ (i) Yellow ppt with K2CrO4 Ba2+ + K2CrO4 → BaCO3 ↓(yellow) + 2K+

(ii) White ppt with (NH4)2SO4 Ba2+ + (NH4)2SO4 → BaSO4 ↓(white) + 2NH4+
Ba2+ + (NH4)2C2O4 → BaC2O4 ↓(white) + 2NH4+
(iii) White ppt with (NH4)2C2O4
Sr2+ (i) White ppt with (NH4)2SO4 Sr2+ + (NH4)2SO4 → SrSO4 ↓(white) + 2NH4+

(ii) White ppt with (NH4)2C2O4 Sr2+ + (NH4)2C2O4 → SrC2O4 ↓(white) + 2NH4+

Ca2+ (i) White ppt with (NH4)2C2O4 Ca2+ + (NH4)2C2O4 → CaC2O4 ↓(white) + 2NH4+

VI Group
Radical Test/Observation/Analysis Reaction
Mg2+ (i) White ppt with NH4OH & Mg2+ + (NH4)2HPO4 + NH4OH→

(NH4)2HPO4 MgNH4PO4 ↓(white) + 2NH4+ + H2O

Zero group (i) All ammonium salts on reacting NH4Cl + NaOH → NaCl + NH3↑ + H2O
(NH4+, PH4+) with base like NaOH, gives smell of
NH3
(ii) Gas evolved NH3 gives white
(ii) NH3 + HCl → NH4Cl ↑ (white fumes)
fumes with NH4OH
(iii) On passing through Hg2(NO3)2, (iii) Hg2(NO3)2 + 2NH3 → Hg (black) +
black colour obtained Hg(NH2)NO3 + NH4NO3

(iv) Brown ppt. is obtained with (iv) 2K2HgI2 + 4KOH + NH4Cl → IHgOHgNH2 +
7KI + KCl.3H2O
nesseler’s reragent
(Iodide solution black or brown ppt)

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