GROUP II CATIONS

Group II Cations: Hg2+ , Pb2+ , Bi3+ , Cu2+ , Cd2+ , As3+ , Sb3+ , and Sn4+.

Precipitating Agent: S= (from thioacetamide in acidic solution)

PROCEDURE II - O

To 2 ml of Group II unknown (or decantant from Procedure I-1) add 6 MNH4OH to make the
solution just alkaline; then add 6 M HCl dropwise till the solution is just acidic; then add .5 ml of HCl in
addition. Add 2 ml of 3% H2O2 and heat; then add 1 drop of NH41. The hydrogen sulfide produced by
the hydrolysis of thioacetamide is a gas. It will tend to escape rapidly from the boiling solution. To get
rapid precipitation add 2-3 drops of thioacetamide every 30 seconds or so; stir and keep the solution in
the hot water bath between additions. Test for complete precipitation and centrifuge. Decantate:
Contains Groups III, IV, and V when working with general unknown; label and save.

ION COLOR OF SOLUTION PRECIPITATED COLOR OF THE

OF ION FORM OF ION PRECIPITATE

Hg2+ Colorless HgS Black

Pb2+ Colorless PbS Black

Bi3+ Colorless Bi2S3 Brown to Black

Cu2+ Blue CuS Black

Cd2+ Colorless CdS Yellow

As3+ Colorless As2S3 Yellow

Sb3+ Colorless Sb2S3 Orange

Sn4+ Colorless SnS2 Yellow

PROCEDURE II-1

Wash the precipitate twice with 2 ml of 1% NH4NO3 to free it from acid. Centrifuge and discard
wash water. Now add 2 ml of 6 M NH4OH to the precipitate; then add 15 drops of thioacetamide. Heat
and stir in water bath for 5 minutes; then centrifuge.

Decantate: (NH4)3AsS3, (NH4)3SbS3, and (NH4)2SnS3, Section IIB.

Precipitate: HgS, PbS, Bi2S3, CuS, CdS, Section IIA.

 SECTION IIA
PROCEDURE IIA-1

To the precipitate from procedure II-1 and 3 ml of 6 M HNO3, heat in water bath; stir and centrifuge.

Decantate: Pb(NO3)2, Bi(NO3)3, Cu(NO3)2, Cd(NO3)2 (Procedure IIA-3)

Precipitate: HgS (black) (Procedure IIA-2)

PROCEDURE IIA-2

Cover the residue (HgS) with 6M HCl and a few crystals of KClO3. Heat in an evaporating dish until
Cl2 is expelled. Apply the starch iodide paper test. (Wet starch iodide paper turns brown to purple in the
presence of Cl2. Dilute the solution with 1 ml of H2O and add a few drops of SnCl2. A white, black or
gray precipitate confirms the presence of Hg22+.

PROCEDURE IIA-3

To the decantate [Pb(NO3)2Bi(NO3)3, Cu(NO3)2, Cd(NO3)2] from Procedure IIA-1 add 1 ml of 6 M

H2SO4 and heat in the hood just until white fumes of H2SO4 appear. (Appearance of white fumes insures
the evaporation of HNO3; PbSO4 is soluble in HNO3.) Cool and dilute with H2O to a volume of 2 ml. A
white precipitate (PbSO4) confirms the presence of Pb2+.

Decantate: Bi2(SO4)3, CuSO4, CdSO4 (Procedure IIA-4)

Precipitate: PbSO4

PROCEDURE IIA-4

To the decantate [Bi2(SO4)3, CuSO4 and CdSO4] from Procedure IIA-3, add 15 M NH4OH until the
solution is strongly alkaline; then add 5 extra drops. Stir for a few minutes; Bi(OH)3 is a white slowly
forming precipitate. (Procedure IIA-5)

Decantate: Cu(NH3)4SO4, Cd(NH3)4SO4 (Procedure IIA-6)

Precipitate: Bi(OH)3

PROCEDURE IIA-5

Wash precipitate twice with 1% NH4OH and discard wash water. To the precipitate, BI(OH)3, add
freshly prepared sodium stannite, NaSn(OH)3 (SEE NOTE 7). The immediate blackening of the original
precipitate confirms the presence of Bi3+.

PROCEDURE IIA-6

Use the decantate from Procedure IIA-4 which may contain Cu(NH3)4so4, Cd(NH3)4SO4 [A blue color
at this point indicates the presence of Cu(NH3)42+]. Divide the decantate into two parts (a) and (b). To
portion (a) just acidify by adding 6 M HOAc; then add 2 drops in excess; now add potassium
hexocyanoferrate K4Fe(CN)6 (also known as potassium ferrocyanide). Pink to purple red precipitate
indicates the presence of Cu2+.
 If Cu2+ is present, [WARNING: Be sure that the 2nd portion of sample (b) is basic; if acidic,
HCN is evolved when NaCN is added, HCN is very poisonous gas.] Add a few drops of NaCN till
blue color disappears [it might be necessary to add solid NaCN] to form dicyanocopper I complex which
will not interfere with the Cd2+ test. At this time the blue color should disappear, indicating the
complexing of all the Cu. Now add a few drops of IM thioacetamide and heat. A yellow precipitate
confirms the presence of Cd2+.

If Cu2+ is absent, then test for Cd2+ as described above but do not add the NaCN.

SECTION IIB
PROCEDURE IIB-7

The decantate from Procedure II-1 contains (NH4)3AsS3, (NH4)3SbS3, (NH4)2SnS3. Add 6 M HCl till
the solution is just acidic; stir, centrifuge and discard decantate.

PRECIPITATE: As2S3, Sb2S3, SnS2

Transfer precipitate As2S3, Sb2S3 and SnS2 to an evaporating dish and heat for a few minutes (do not
boil) with 3 ml of 6 MHCl until H2S is completely expelled. Apply lead acetate paper test. (Wet lead
acetate paper turns brown to black in the presence of H2S.) Centrifuge and save decantate.

Decantate: SnCl62-, SbCl63-, colorless (Procedure IIB-9)

Precipitate: As2S3, yellow (Procedure IIB-8)

PROCEDURE IIB-8

Wash residue with 10 drops of H2O added to 3 drops of 3 M HCl, centrifuge and discard wash water.
Dissolve the residue (As2S3) in 1 ml of concentrated HNO3 and warm till brown fumes fail to appear [all
solid should dissolve; any precipitate might be discarded]. Add 2 ml of (NH4)2MoO4 and heat; yellow
precipitate confirms the presence of As3+. (A white precipitate in the absence of As3+ is due to the
decomposition of (NH4)2MoO4 and is not to be confused with the test for the As3+).

PROCEDURE IIB-9

Use the decantate from Procedure IIB-7 [SnCl62-, SbCl63-]. Divide the solution into two parts (a) and
(b). Pour solution (a) onto a piece of tin on a clean silver coin (if the coin is not clean, wash with 3 M
HNO3 for a few seconds and wash with distilled water). A fine black deposit on the coin confirms the
presence of Sb. This precipitate is insoluble in NaOCl solution. Any arsenic which might have
precipitated is soluble in NaOCl.

To part (b) add an equal volume of HCl and a piece of Mg ribbon 3 inches long. Allow all the Mg to
dissolve completely; remove any Mg which did not dissolve from the test tube at this point. Then add
two drops of HgCl2. A white, black or gray precipitate which develops after several minutes confirms the
presence of Sn2+.
NOTES

1. The sulfides HgS, CuS, Bi2S3, PbS, CdS exhibit basic properties while AS2S3,, SnS3, Sb2S3
exhibit acidic properties; thus treating the sulfides of Group II cations with a base dissolve the
solids that exhibit acidic properties.

2. The addition of NH4OH and HCl to the unknown of Group II cations is to control the pH, the S=
varies inversely with the square root of H+. If a large excess of HCl is added, some cations of
Group II will not precipitate (the greater the H+, the smaller the S=). The H+ concentration
needed to regulate the [S=] is .2 - .3 M.

3. H2O2 is added to oxidize Sn2+ to Sn+4.

4. NH4I is added to reduce As5+ to As3+.

5. The unknown might turn cloudy when diluted or when NH4OH is added. This cloudiness is due
to the formation of BiOCl or SbOCl. The solution should clear up when HCl is added.
Regardless of whether the solution clears or not, the cations of Group II will precipitate as
sulfides when thioacetamide is added.

6. KClO3 is added to oxidize Sn2+ to Sn+4 and the HCl is added to form SnCl42-, and HgCl42-
according to the following equations:

HgS + HCl + KClO3 (HgCl4)2- + S + H2O

2Hg
SnCl42- + Hg2Cl2 + SnCl62-
black

Hg 2 Cl 2
SnCl42- + 2HgCl42- + SnCl62- + 4Cl=
white
7. To prepare a solution NaSN(OH)3, add NaOH to SnCl2 till a white precipitate forms, then add
NaOH dropwise while stirring till the precipitate dissolves.

NaOH + SnCl2 Sn(OH)2 (White Precipitate)

Sn(OH)2 + NaOH NaSN(OH)3 (Clear)

8. Section IIB

H2S is expelled so that it will not react with the cations of Group IIB.

9. Mg is added to reduce antimony ion to metallic antimony and Sn4+ to Sn2+.

Precipitation of Group II Cations

Hg2+ + S= HgS

Pb2+ + S= PbS

Bi3+ + S= Bi2S3

Cu2+ + S= CuS
 Cd2+ + S= CdS

As3+ + S= As2S3

Sb3+ + S= Sb2S3

Sn4+ + S= SnS2

PROCEDURE II-1

As2S3 + NH4OH + H2S (NH4)3AsS3) Ammonium thioarsenite

Sb2S3 + NH4OH + H2S (NH4)3SbS3 Ammonium thioantimonite

SnS2 + NH4OH + H2S (NH4)2SnS3 Ammonium thiostannate

PROCEDURE IIA-1

3PbS + 2NO3- + H+ 3Pb2+ + 3S + 2NO + 4H2O

Bi2S3 + 2NO3- + H+ 2Bi3+ + 3S + 2NO + 4H2O

3CuS + 2NO3- + H+ 3Cu2+ + 3S + 2NO + 4H2O

3CdS + 2NO3- + H+ 3Cd2+ + 3S + 2NO + 4H2O

PROCEDURE IIA-2

aqua HgCl 4 2− Hg 2 Cl 2 Hg
HgS + + SnCl2 +
regia colorless white black

PROCEDURE IIA-3

Bi2(OH)3 + NH4OH Bi(OH)3

CuSO4 + NH4OH Cu(NH3)4SO4

CdSO4 + NH4OH Cd(NH3)4SO4

Bi
Bi2(OH)3 + NaSn(OH)3 + Na2SN(OH)6
black

PROCEDURE II-A

Cu(NH3)42(+) + K4Fe(CN)6 Cu2Fe(CN)6 Pink

Blue cupric ferrocyanide
or copper hexacyanoferrate II

Cd(NH3)42+ + K4Fe(CN)6 CdFe(CN)6 White

cadium hexacyanoferrate II
or cadium ferrocyanide

Cu2+ + CN- Cu(CN3)2- complex ion does not interfere with the test for Cd2+
 Cd2+ + CN- Cu(CN)32-
Cd2+ + S= CdS Yellow

PROCEDURE Section IIB

As2S3 + HCl As2S3 Yellow Precipitate

Sb2S3 + HCl [SbCl4]-

SnS2 + HCl [SnCl6]2-

PROCEDURE IIB-8

Sb
(SbCl4)- + Sn + SnCl4=
black

Sb
SbCl63- + Mg + Mg2+ + Cl-
black

SnCl62- + Mg SnCl4= + Mg2+ + Cl-

Hg 2 Cl 2
SnCl42- + HgCl2 + SnCl6=
white

Hg
Hg2Cl2 + SnCl4= + SnCl6=
black