Scheme for Analysis of group I (Ag+, Pb2+& Hg22+)

Solution containing All groups:

Solution + slight excess cold dilute HCl, centrifuge

White ppt Centrifugate

(Group I Chlorides: PbCl2↓, AgCl↓, Hg2Cl2↓) (Groups: II-VI)

Add hot water, centrifuge

Centrifugate White ppt

(Pb2+) (AgCl↓& Hg2Cl2↓)

+2NH3 (dilute ammonia), centrifuge

Divide into 4 portions:
(1) Cool → PbCl2 ↓White ppt
(2) + SO42-→PbSO4↓ White ppt
(3) + 2I- → PbI2↓ Bright yellow ppt
(4) + CrO42- → PbCrO4 ↓Yellow ppt Gray ppt Soluble complex
o
(Hg ↓+ HgNH2Cl ↓) [Ag(NH3)2]+ Cl-
Black & White Colorless

Aqua Regia (HCl:HNO3)

+ I- + 2H+ (dil HNO3)

soluble mercuric Yellow ppt
chloride (HgCl2) White ppt
(AgI ↓)
(AgCl↓)
Divide into 2 portions:
(1) + SnCl2-→Hg2Cl2↓ White ppt + 2NH3 + Cl-
(2) + 2I- → HgI2↓ (scarlet red) ppt + 2NH4+
HgI2↓ + 2I- → [HgI4]2- (soluble complex)

Why do we use cold HCl?

Because PbCl2 is soluble on hot.
Why do we use dilute HCl?
Because PbCl2 is soluble in conc HCl forming a soluble complex:
PbCl2 + 2Cl- → [PbCl4]2-
Why do we avoid large excess HCl?
Because PbCl2 is soluble in excess HCl forming a soluble complex:
PbCl2 + 2Cl- → [PbCl4]2-