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 original precipitate confirms the presence
of Bi3+. Wash residue with 10 drops of H2O
PROCEDURE IIA-1 added to 3 drops of 3 M HCl, centrifuge
PROCEDURE IIA-6 and discard wash water. Dissolve the
To the precipitate from procedure II-1 residue (As2S3) in 1 ml of concentrated
and 3 ml of 6 M HNO3, heat in water bath; Use the decantate from Procedure IIA- HNO3 and warm till brown fumes fail to
stir and centrifuge. 4 which may contain Cu(NH3)4so4, appear [all solid should dissolve; any
Cd(NH3)4SO4 [A blue color at this point precipitate might be discarded]. Add 2 ml
Decantate: Pb(NO3)2, Bi(NO3)3, Cu(NO3)2, indicates the presence of Cu(NH3)4 ]. of (NH4)2MoO4 and heat; yellow
2+

Cd(NO3)2 (Procedure IIA-3) Divide the decantate into two parts (a) and precipitate confirms the presence of As3+.
(b). To portion (a) just acidify by adding 6 (A white precipitate in the absence of As3+
Precipitate: HgS (black) (Procedure IIA-2) M HOAc; then add 2 drops in excess; now is due to the decomposition of (NH4)2MoO4
add potassium hexocyanoferrate and is not to be confused with the test for
PROCEDURE IIA-2 K 4Fe(CN) 6 (also known as potassium the As3+).
ferrocyanide). Pink to purple red
Cover the residue (HgS) with 6M HCl precipitate indicates the presence of Cu . PROCEDURE IIB-9
2+

and a few crystals of KClO3. Heat in an

evaporating dish until Cl2 is expelled. If Cu2+ is present, [WARNING: Be Use the decantate from Procedure IIB-
Apply the starch iodide paper test. (Wet sure that the 2nd portion of sample (b) is 7 [SnCl 6 , SbCl6 ]. Divide the solution
2- 3-

starch iodide paper turns brown to purple
in the presence of Cl2. Dilute the solution NaCN is added, HCN is very poisonous
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 drops of IM thioacetamide and heat. A
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 PRECIPITATE: As2S3, Sb2S3, SnS2
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 8)
sodium stannite, NaSn(OH)3 (SEE NOTE
7). The immediate blackening of the
basic; if acidic, HCN is evolved when
gas.] Add a few drops of NaCN till blue
color disappears [it might be necessary
add solid NaCN] to form dicyanocopper I distilled water). A fine black deposit on
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 is soluble in NaOCl.
yellow precipitate confirms the presence of
Cd 2+
. HCl
If Cu2+ is absent, then test for Cd2+ as
described above but do not add the NaCN. dissolve from the test tube at this point.
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.
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-
PROCEDURE IIB-8
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
to HNO3 for a few seconds and wash with
the coin confirms the presence of Sb. This
precipitate is insoluble in NaOCl solution.
Any arsenic which might have precipitated
To part (b) add an equal volume of
and a piece of Mg ribbon 3 inches
long. Allow all the Mg to dissolve
completely; remove any Mg which did not
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 Sb2S3 + NH4OH + H2S (NH4)3SbS3 PROCEDURE Section IIB
BiOCl or SbOCl. The solution should Ammonium thioantimonite
clear up when HCl is added. Regardless As2S3 + HCl As2S3 Yellow
of whether the solution clears or not, the SnS2 + NH4OH + H2S (NH4)2SnS3 Precipitate
cations of Group II will precipitate as Ammonium thiostannate
sulfides when thioacetamide is added. Sb2S3 + HCl [SbCl4]-
PROCEDURE IIA-1
6. KClO3 is added to oxidize Sn2+ to Sn+4 SnS2 + HCl [SnCl6]2-
and the HCl is added to form SnCl42-, and 3PbS + 2NO3 + H
- +
3Pb + 3S +
2+

HgCl42- according to the following 2NO + 4H2O PROCEDURE IIB-8

equations:
Bi2S3 + 2NO3- + H+ 2Bi3+ + 3S + Sb
HgS + HCl + KClO3 (HgCl4) + S +
2-
2NO + 4H2O (SbCl4)- + Sn + SnCl4=
H2O
black
3CuS + 2NO3- + H+ 3Cu2+ + 3S +
2Hg 2NO + 4H2O Sb
SnCl42- + Hg2Cl2 + SnCl62- SbCl63- + Mg + Mg2+ +
black black
3CdS + 2NO3- + H+ 3Cd2+ + 3S + Cl-
2NO + 4H2O
Hg 2 Cl 2 SnCl62- + Mg SnCl4= + Mg2+ + Cl-
SnCl42- + 2HgCl42- +
white PROCEDURE IIA-2
SnCl6 + 4Cl
2- =
Hg 2 Cl 2
2− SnCl42- + HgCl2 +
aqua HgCl 4 white
7. To prepare a solution NaSN(OH)3, add HgS + +
regia colorless SnCl6=
NaOH to SnCl2 till a white precipitate
forms, then add NaOH dropwise while Hg 2 Cl 2 Hg
stirring till the precipitate dissolves. SnCl2 + Hg
white black Hg2Cl2 + SnCl4= +
black
NaOH + SnCl2 Sn(OH)2 (White SnCl6=
Precipitate) PROCEDURE IIA-3

Sn(OH)2 + NaOH NaSN(OH)3 Bi2(OH)3 + NH4OH Bi(OH)3

(Clear)
CuSO4 + NH4OH Cu(NH3)4SO4
8. Section IIB
CdSO4 + NH4OH Cd(NH3)4SO4
H2S is expelled so that it will not react
with the cations of Group IIB. Bi
Bi2(OH)3 + NaSn(OH)3 +
black
9. Mg is added to reduce antimony ion to Na2SN(OH)6
metallic antimony and Sn4+ to Sn2+.
PROCEDURE II-A
Precipitation of Group II Cations
Cu(NH3)42(+) + K4Fe(CN)6
Hg2+ + S= HgS Cu2Fe(CN)6 Pink
Blue cupric
Pb2+ + S= PbS ferrocyanide
or copper
Bi3+ + S= Bi2S3 hexacyanoferrate II

Cu2+ + S= CuS Cd(NH3)42+ + K4Fe(CN)6 Techniques

Cd2+ + S= CdS CdFe(CN)6 White In this lab, you will perform simple test
cadium tube experiments and make careful
As3+ + S= As2S3 hexacyanoferrate II observations. To separate ions of each
or cadium group, you will form an insoluble
Sb3+ + S= Sb2S3 ferrocyanide precipitate and centrifuge to remove solid
from the ions that remain in solution. You
Sn4+ + S= SnS2 Cu2+ + CN- Cu(CN3)2- will need to carefully wash the precipitate
complex ion does not interfere with and decant the solution to remove all
PROCEDURE II-1 the test for Cd2+ soluble ions. You will use pH paper when
you acidify and basify your samples.
As2S3 + NH4OH + H2S (NH4)3AsS3) Cd2+ + CN- Cu(CN)32- Finally, you will heat in a water bath to
Ammonium thioarsenite Cd2+ + S= CdS Yellow perform some reactions. Be sure to use
clean glassware to avoid contamination of
your sample. Wash glassware with soap excess of ammonium hydroxide in the
and rinse with distilled water. original salt solution. A resulting blue
color indicates the presence of Cu2+, and a
2nd analytical group of cations white precipitate indicates bismuth.
The 2nd analytical group of cations Otherwise, if the precipitate is insoluble
consists of ions that forms acid-insoluble then Hg2+ is present.
sulfides. Cations in the 2nd group include: To distinguish between ions in the yellow
Cd2+, Bi3+, Cu2+, As3+, As5+, Sb3+, precipitate, an excess of NaOH is added to
Sb5+, Sn2+, Sn4+ and Hg2+. Pb2+ is the original salt solution to form a white
usually also included here in addition to precipitate. The test tube is then shaken,
the first group. and if the white precipitate dissolves, then
The reagent can be any substance that Sn4+ is present; otherwise, Cd2+ is
gives S2− ions in such solutions; most present.
commonly used are H2S (at 0.2-0.3 M), Confirmation test for lead:
AKT (at 0.3-0.6 M). The test with the Pb2+ + 2 KI → PbI2 + 2 K+
sulfide ion must be conducted in the Pb2+ + K2CrO4 → PbCrO4 + 2 K+
presence of dilute HCl. Its purpose is to Confirmation test for copper:
keep the sulfide ion concentration at a 2 Cu2+ + K4[Fe(CN)6] + CH3COOH →
required minimum, so as to allow the Cu2[Fe(CN)6] + 4 K+
precipitation of 2nd group cations alone. If Cu2+ + 2 NaOH → Cu(OH)2 + 2 Na+
dilute acid is not used, the early Cu(OH)2 → CuO + H2O (endothermic)
precipitation of 4th group cations (if Confirmation test for bismuth:
present in solution) may occur, thus Bi3+ + 3 KI (in excess) → BiI3 + 3 K+
leading to misleading results. Acids beside BiI3 + KI → K[BiI4]
HCl are rarely used. Sulfuric acid may lead Bi3+ + H2O (in excess) → BiO+ + 2 H+
to the precipitation of the 4th group Confirmation test for mercury:
cations, while nitric acid directly reacts Hg2+ + 2 KI (in excess) → HgI2 + 2 K+
with the sulfide ion in the reagent, forming HgI2 + 2 KI → K2[HgI4] (red precipitate
colloidal sulfur. dissolves)
The precipitates of these cations are almost 2 Hg2+ + SnCl2 → 2 Hg + SnCl4 (white
indistinguishable, except for CdS which is precipitate turns gray)
yellow. All the precipitates, except for
HgS, are soluble in dilute nitric acids. HgS
is soluble only in aqua regia, which can be
used to separate it from the rest. The action
of ammonia is also useful in differentiating
the cations. CuS dissolves in ammonia
forming an intense blue solution, while
CdS dissolves forming a colourless
solution. The sulfides of As3+, As5+,
Sb3+, Sb5+, Sn2+, Sn4+ are soluble in
yellow ammonium sulfide, where they
form polysulfide complexes.
This group is determined by adding the salt
in water and then adding dilute
hydrochloric acid followed by hydrogen
sulfide. Usually it is done by passing
hydrogen sulfide over the test tube for
detection of 1st group cations. If it forms a
reddish brown or black precipitate then
Bi3+, Cu2+, Hg2+ or Pb2+ is present.
Otherwise, if it forms a yellow precipitate,
then Cd2+ or Sn4+ is present; or if it forms
a brown precipitate, then Sn2+ must be
present; or if a red orange precipitate is
formed, then Sb3+ is present.
To distinguish between ions in the black or
reddish brown precipitate, it is first boiled
in diluted HNO3. If it is insoluble, then
Hg2+ is present. If it is soluble, then Cu2+,
Hg2+ or Pb2+ may be present; sulfuric
acid is then added to the resulting solution.
If a white precipitate forms, then Pb2+
may be present; if no precipitate is formed,
then a new solution is made by adding an