EXPERIMENT 5: REACTIONS OF THE HYDROGEN SULFIDE GROUP

5-1 5-1a Reactions with Hydrogen Sulfide 5-1b Solubility in Na2S

Ions Formula Color & Nature reagent
Pb+2 PbS black insoluble
dark-brown or
Bi+3 Bi2S3 insoluble
brownish-black
Cu+2 CuS black insoluble
Cd+2 CdS yellow insoluble
HgS white yellow
Generally. the precipitate is
insoluble in water, hot
brown black
(initially a white precipitate of Na2HgS2
dilute nitric acid, alkali
mercury(II) chlorosulphide soluble colorless soln
hydroxides, or (colourless)
Hg+2 forms, which reacts with (sodium sulphide (2M) dissolves
ammonium sulphide
further amounts of hydrogen the precipitate when the complex
sulphide and finally a black ion is formed)
Aqua regia (1:3 HNO3 and
conc H2SO4) dissolves the precipitate of mercury(II)
precipitate sulphide is formed)
Sb2S3
(The precipitate is soluble in orange or reddish- Na3SbS4
Sb+3
warm concentrated orange soluble colorless soln
hydrochloric acid)
As2S3
(The precipitate is insoluble
in concentrated
hydrochloric acid Na3AsS4
As+3 yellow
(distinction and method of soluble colorless soln
separation from Sb2S3 and
SnS2), but dissolves in hot
concentrated nitric acid)
Na2SnS3
Sn+2 SnS light-brown
soluble colorless soln
Na2SnS3
Sn+4 SnS2 yellow
soluble colorless soln
Notes:
Cations of the second group are traditionally divided into two sub-groups; the copper sub-group and the arsenic sub-
group. The basis of this division is the solubility of the sulphide precipitates in ammonium polysulphide. While sulphides
of the copper sub-group are insoluble in this reagent, those of the arsenic sub-group do dissolve with the formation of
thiosalts

The chlorides, nitrates, and sulphates of the cations of the copper subgroup are quite soluble in water. The sulphides,
hydroxides, and carbonates are insoluble. Some of the cations of the copper sub-group (mercury (II), copper (II), and
cadmium (II) tend to form complexes (ammonia, cyanide ions, etc.). According to Gilreath (1954), these cations exhibit
basic properties hence forming insoluble precipitate upon the addition of KOH.

The arsenic sub-group consists of the ions arsenic (III), arsenic (V), antimony (III), antimony (V), tin (II) and tin (IV). These
ions have amphoteric character: their oxides form salts both with acids and bases (Vogel, 1996). According to Gilreath
(1954), these cations exhibit acidic properties hence forming soluble precipitate upon the addition of KOH

Confirmatory TESTS

Ions Reagents Formula Color & Nature

a) K2Cr04 PbCrO4 yellow
5-2 Pb+2
b) excess NaOH Na2PbO2 or Pb(OH)4-2 yellow soln
5-3 Bi+3
BiO
Bismuth is converted first into
In the presence of
the hydroxide form (Bi(OH)3)
bismuth the reaction is
upon addition of ammonia, Na2SnO2 black
accelerated with stannite
while cupric and cadmium in
ion; hence bismuth is
the ammonia complex form
precipitated
(Cu(NH3)42+ and Cd(NH3)42+)
5-4 Cu+2 a) K4Fe(CN)6 Cu2Fe(CN)6 amorphous reddish-
 (remember: brown
ferrOcyanide) (insoluble in dilute acids)
b) NH4OH Cu(OH)NO3 green basic salt
Cu(NH3)4+2 or
c) excess NH4OH blue soln
Cu(NH3)4(OH)2
5-5 Cd+2 K4Fe(CN)6 Cd2Fe(CN)6 white

Ions Reagents Formula Color & Nature

white gray
(when added in moderate
amounts: white, silky
precipitate of mercury(I)
Hg2Cl2 HgO
chloride (calomel); If more
(only stannous ion will
a) SnCl2 reagent is added, mercury(I)
give the characteristic
chloride is further reduced
result for mercuric ion)
and black
5-6 Hg+2 precipitate of mercury is
formed)
Disproportionation
b) KI HgI2 scarlet red
soluble colorless soln
c) excess KI K2HgI4 or HgI4-2
(formation of complex)
Hg Silvery white deposit
d) copper coin (reduces mercury(II) ions
(Amalgam)
to the copper metal)
black
(formation of Sn-Ag couple
a) Ag coin + Tin SbO
5-7 Sb+3 hence formation of antimony
metal)
b) NaOBr --- insoluble
colorless gas +
5-8 As+3 NaOH, Al metal, AgNO3 AsH3 (arsine gas) + AgO
black
Hg2Cl2 HgO
+2
5-9 Sn HgCl2 Disproportionation white gray
reaction
colorless soln
a) Mg metal + HCl Sn+2 (converts the chlorstannate
to the stannous form)
Sn+4
Hg2Cl2 HgO
b) HgCl2 Disproportionation white gray
reaction

Ref: Vogel, A. I. (1996). Vogels Qualitative Inorganic Analysis.

Gilreath, E.S. (1954). Qualitative Analysis using Semi micro Methods.