I.

Introduction
Chemical analysis can either be qualitative or quantitative in nature. In qualitative analysis we
work to identify the substances present in a given sample. We are not concerned with the quantity of
each substance, but only whether certain substances are present or absent. The techniques used in
qualitative analysis depend upon the material being analyzed. The techniques you will learn can be used
to identify ions occurring in other types of samples such as minerals, ground water and industrial waste
streams.
The qualitative analysis of ions in a mixture must follow a scheme that can be summarized as
follows: (1) Ad reagents that can exploits the more general properties of ions to separate major groups of
ions; (2) Separate major groups into subgroups with reaction that will distinguish less general properties;
and (3) Add reagents that will specifically confirm the presence of individual ions. Following this
general three-step plan, several different analytical schemes have been devised that are based on various
ways of defining major groups.
In qualitative analysis it is important to run your analytical scheme on known samples,
prepared to contain specific ions of interest, as well as unknown samples in order to test your ability to
use the procedure to analyze a solution of unknown composition.

II.

Objectives
The group observed and recorded carefully the chemical behavior of Group II cations
with different reagents.

III.

Materials
Test tubes
Test tube rack
Stirring rod
10 mL graduated cylinder
250 mL beaker
Water bath

Blue litmus paper

Wash bottle
Hot plate
Centrifuge balance
Dropper

Chemicals:
Thioactemide (CH3CSNH2)
6M Hydrochloric Acid (HCl)
Ammonium Acetate (NH4C2H3O2)
6M Sodium Hydroxide (NaOH)
Sodium dithionite (Na2S2O4)
IV.

6M Ammonium Hydroxide (NH4OH)

6M Nitric Acid (HNO3)
1M Potassium Chromate (K2CrO4)
0.1M Tin(II) Chloride (SnCl2)
0.1M Potassium ferrocynanide (K4Fe(CN)6)

Procedure
Step 1: The group added 15 drops of concentrated NH4OH to the precipitate. We tested the pH
with red litmus paper to determine if it is alkaline. When solution is not alkaline, we added 6M NH4OH
until it is alkaline to red litmus paper. We added 6M HCl dropwise until the solution is barely acidic to
blue litmus paper. We went to the hood and added 1mL of thioacetamide. We heated the solution for five
minutes in a boiling water bath in the fume hood. We lightly cork the test tube and centrifuged the
solution for approximately 1 minute to remove the Group II sulfide precipitates. We saved the
supernatant for further testing of Group III, IV and V.
Step 2: We washed the precipitate in Step 1 with 3 mL distilled H2O to ensure that it was free
from Cl- ion. We shook the tube vigorously to remove the precipitate. We centrifuged and discarded the
supernatant.

Step 3: To the precipitate in Step 2, we added 1 mL H2O and shook it vigorously to suspend the
precipitate. We added 1 mL of 6M HNO3 to the suspended sulfides. We heated the mixture gently for 5
minutes to ensure the Group II sulfides, except HgS, have been dissolved by HNO 3. If HgS is present, a
precipitate should remain. If all the precipitate dissolves, then there was no HgS present. We cooled the
solution in cold tap water and centrifuged for 1 minute. We decanted the supernatant to a new test tube
and saved it for isolating other Group II cations.
If a dark colored precipitate remains, it is indicative of HgS. It is possible to miss HgS
though, if it is obscured be nearly white free sulfur or if HgS has been converted into a light colored
double salt Hg(NO3)22HgS by HNO3. Therefore, if a precipitate remains after dissolution by HNO 3 in
Step 1, the confirmatory test for Hg should be carried out on the precipitate.
Step 4: Confirmatory test for Mercury
To the precipitate in Step 3, we added 6M HNO3 and 6M H2O. This makes aqua regia
royal water. We heated it in a boiling water bath until the reaction was complete. A small ball of sulfur
remained and we removed it using a glass stirring rod. We centrifuged and discarded the precipitate. To
the aqua regia above, we added 1 mL of distilled water and transferred all the solution to an evaporating
dish. In the hood, we carefully heated the solution on a hotplate and evaporated it to the size of a quarter.
It is important not to evaporate the solution to dryness as the Hg2Cl2 is volatile and maybe lost. We
cooled the solution in evaporating dish and divided it into two. To the half solution, we added 0.5 mL of
0.1M SnCl2. A white precipitate of Hg2Cl2 indicates the presence of Hg2+. This precipitate turned dark or
grey with time as the Hg2+ was reduced to free Hg by excess of Sn2+. To the other half of the solution, we
immersed a piece of heavy copper wire for a couple of minutes. If mercury is present, it will be
deposited as shiny liquid mercury on the copper wire as Hg2Cl2 was reduced to free Hg.
Step 5: Confirmatory test for Lead
To the supernatant in Step 3, we added 3 drops of concentrated NH 4OH and 10 drops of
saturated ammonium sulfate solution. The precipitate formed indicates the presence of lead. We
centrifuged the solution and separated the precipitate from the supernatant. The precipitate was tested for
the presence of lead and we saved the supernatant for other Group II cation.
Step 6: Optional: Test to ensure what is isolated is of lead.
We dissolved the precipitate by 0.5 mL NH 4C2H3O2. To the resultant solution, we added 2
drops of K2CrO4. A yellow precipitate of PbCrO4 indicates the presence of lead.
Step 7: To the supernatant in Step 5, we added concentrated NH4OH until it was alkaline to red
litmus paper. When it was alkaline, we added 3-5 drops of excess concentrated NH 4OH. The appearance
of a deep blue color in the solution indicates the presence of copper amine complex, Cu(NH 3)42+. A white
precipitate of Bi(OH)3 is most likely to be formed because a small amount of precipitate may be masked
by a large amount of Cu(NH3)42+. We gently warmed the solution, centrifuged and checked the presence
of precipitate. The presence of a white precipitate is indicative of Bi(OH)3. We proceeded for the
confirmatory test for bismuth and kept the supernatant for further testing of Group II cations.
Step 8: Confirmatory test for the presence of Bismuth
We washed the precipitate in Step 7 twice with 1 mL water. We centrifuged and discarded
the wastes. We prepared a fresh solution of sodium stannite by adding 6M NaOH dropwise to 2 mL of
0.1M SnCl2. A thick white precipitate of Sn(OH) 2 formed and persisted. We added 6M NaOH dropwise
to dissolve the precipitate and it gave a strongly basic solution. When all the precipitate dissolved,
sodium stannite can already be use. We added all the freshly prepared sodium stannite to the white
precipitate from Step 7. Sodium stannite acted as a reducing agent and reduced Bi 3+ to metallic Bi
causing the precipitate to turn black.
Step 9: When the supernatant in Step 7 is blue, it was indicative of the presence of Cu 2+. The
presence of Cd2+ however, cannot be ruled out, as its clear color would be masked by the presence of

Cu2+. The absence of a blue color indicates the absence of Cu 2+ but does not confirm the presence of
Cd2+. When the solution was clear, we proceeded with the confirmatory test for Cd 2+ (). When the
solution was blue, we tested it for both copper and cadmium ().
Step 10: We removed a few drops from the solution in Step 9 to another test tube and saved it for
the second confirmation test for copper. To the remaining solution, we added a pinch of Na 2S2O4 and
heated it for 5 minutes in a boiling water bath. We observed the color of the precipitate formed. When no
precipitate formed or when the solution remains faintly blue, we added a little more Na 2S2O4 and
reheated it. The presence of a dark precipitate indicated the reduction of Cu2+ to metallic copper.
Step 11: Confirmatory of Cadmium
We decanted the supernatant into another test tube and tested it for the presence of
cadmium. To this solution, we added 5 drops of thioacetamide and heated it for 5 minutes in a boiling
water bath. The presence of a yellow precipitate was CdS. When a dark precipitate occurred and coppe
was found previously, these was the residual copper forming the CuS precipitate. When it occurred, we
dissolved the precipitate in HNO3, neutralized it and then made it basic and then we repeated the
ditionite treatment again to test cadmium.
Step 12: Confirmatory test for Copper
To the saved solution in Step 10, we added 6M acetic acid dropwise until the solution
became acidic to blue litmus paper. When it was acidic, we added a few drops of 0.1M K 4Fe(CN)6. A
maroon precipitate indicates the presence of copper.
V.

Data and Observation

A. Group II Flow Chart

B. Observations and reactions

Confirmation test for Mercury

a. Dissolution of HgS by HNO3.

o HgS(aq) + HNO3(aq) Hg(NO3)2(s)(Dark Color) + HS(aq)
HgS may be converted into a light colored double salts Hg(NO3)22HgS
o HgS(aq) + HNO3(aq) Hg(NO3)22HgS(s)
b. Dissolution of HgS by aqua regia.
o 3HgS + 6Cl- + 2NO3- + 8H+ 3HgCl2(aq) + 3S + 2NO + 4H2O
c. Addition of Tin(II) Chloride
HgCl2 + SnCl2 Hg2Cl2(s)(White) + Hg(s)(Black) + Sn4+

Confirmatory test of Bismuth

a. Removing Bi3+ from solution by adding NH4OH
o Bi3+(aq) + 3NH4OH(aq) Bi(OH)3(s) + 3 NH4(aq)
b. Preparation of Sodium Stannite (NaSn(OH)3-)
o 2NaOH(aq) + SnCl2(aq) Sn(OH)2(s) + 2NaCl(aq)
Futher addition of NaOH to Sn(OH)2(s) to give a strong basic solution
o Sn(OH)2(s) + NaOH(aq) Sn(OH)3-(aq) + Na+(aq)
c. Bi3+ ion was reduced to black bismuth metal
o Bi(OH)3(s) + 2 Sn(OH)3-(aq) + 3 OH-(aq)
2Bi(s)(Black) + 3 Sn(OH)62-(aq)

Confirmatory test of Lead

a. Addition of (NH4)2SO4
o PbS(s) + (NH4)2SO4 PbSO4(s) + 2NH4+(aq) + S2+(aq)
b. Dissolution of PbSO4 by NH4C2H3O2
o PbSO4(s) + NH4C2H3O2(aq) Pb(C2H3O2)2(s) + (NH4)2SO4(aq)
c. Reprecipitation with K2CrO4
o Pb(C2H3O2)2(s) + K2CrO4(aq)
PbCrO4(aq)(Yellow) + 2KC2H3O2(aq)

Confirmatory of Cadmium

o CdS(aq) + CH3CSNH2(aq)
CdS(s)(Yellow)
a. When a dark precipitate occurred and copper was found previously,
this was the residual copper forming the CuS precipitate. We dissolved
the precipitate in HNO3, neutralized it and then made it basic and then
we repeated the dithionite treatment again to test for cadmium.

Confirmation test for Copper

First confirmation test

a. Addition of NH4OH
o Cu2+ (aq) + 4 NH3(aq) Cu(NH3)42+(aq)(Deep blue)

2
Second confirmation test
b. Addition of 6M acetic acid
o CuS(aq) + CH3COOH(aq) Cu(CH3COO-)2(aq) + H2S(aq)
c. Addition of K4Fe(CN)6
o Cu(CH3COO-)2(aq) + K4Fe(CN)6(aq) Cu2Fe(CN)6(s)(Maroon)
+ CH3COO-(aq) + 4K+(aq)

VI.

Results and Discussion

In the systematic separation of cations, we performed successive separation of group cations
with the used of group reagents. Group reagents react with corresponding group cations and converted
them into insoluble salts like chlorides, sulfides and carbonates. First, we prepared a solution of the
given mixture, then we added group reagent of Group 1 which converted the cations in Group 1 into
insoluble chlorides and separated them as precipitates and then we started to test for Group II cations.
In confirming the presence of mercury, we added 6 drops of concentrated 6M HNO 3 and 6
drops of 6M HCl to dissolve HgS. The resultant HgCl2 was used to confirm the presence of mercury. The
reaction equation was:
3HgS + 6Cl- + 2NO3- + 8H+ 3HgCl2(aq) + 3S + 2NO + 4H2O

We added SnCl2 (Stannous Chloride) to the resultant HgCl2. Sn2+ was oxidized to Sn4+ and
disproportionation occurred when HgCl2 was reduced to Hg2Cl2(s) (white) and Hg(s) (black).
HgCl2 + SnCl2 Hg2Cl2(s)(White) + Hg(s)(Black) + Sn4+
In confirming the presence of bismuth, we added NH4OH to the solution to remove Bi3+ from
other Group II cations.
Bi3+(aq) + 3NH4OH(aq) Bi(OH)3(s) + 3 NH4(aq)
Bi3+ forms a white precipitate Bi(OH)3 while Cu2+ and Cd2+ remained in the solution. Reaction of
Bi(OH)3 with sodium stannite gives rise to black elemetal bistmuth.
Bi(OH)3(s) + 2 Sn(OH)3-(aq) + 3 OH-(aq) 2Bi(s)(Black) + 3 Sn(OH)62-(aq)
In confirming the presence of lead, we added NH4OH to remove Pb2+ from other Group II
cations. The PbSO4 precipitate was then dissolved by adding ammonium acetate ((NH4)2SO4) and then the lead
precipitated out as yellow PbCrO4 upon reaction with K2CrO4.
(1) PbS(s) + (NH4)2SO4 PbSO4(s) + 2NH4+(aq) + S2+(aq)
(2) PbSO4(s) + NH4C2H3O2(aq) Pb(C2H3O2)2(s) + (NH4)2SO4(aq)
(3) Pb(C2H3O2)2(s) + K2CrO4(aq) PbCrO4(aq)(Yellow) + 2KC2H3O2(aq)
In confirming the presence of cadmium, we added thioacetamide and heated it for five minutes in
a boiling water bath. The presence of a yellow precipitate was CdS. When a dark precipitate occurred and
copper was found previously, this was the residual copper forming the CuS precipitate. We dissolved the
precipitate in HNO3, neutralized it and then made it basic and then repeat the dithionite treatment again to test
for cadmium.
CdS(aq) + CH3CSNH2(aq)

CdS(s)(Yellow)

In the first confirmation test for copper, we added excess concentrated NH4OH. The appearance
of deep blue color indicates the presence of copper amine complex, Cu(NH3)42+.
Cu2+ (aq) + 4 NH3(aq) Cu(NH3)42+(aq)(Deep blue)
In the second confirmation test for copper, we added 6M acetic acid to make it acidic to blue
litmus paper. When it was acidic, we added a few drops of 0.1M K 4Fe(CN)6. A maroon precipitate indicates the
presence of copper.
CuS(aq) + CH3COOH(aq) Cu(CH3COO-)2(aq) + H2S(aq)
Cu(CH3COO-)2(aq) + K4Fe(CN)6(aq) Cu2Fe(CN)6(s)(Maroon) + 2CH3COO-(aq) + 4K+(aq)
In the experiment, the group used 1M CuSO4 as the known sample to confirm the presence of
copper. The procedure was the same in the second confirmatory test for copper. The reaction equation was:
CuSO4(aq) + CH3COOH(aq) Cu(CH3COO-)2(aq) + H2SO4(aq)
Cu(CH3COO-)2(aq) + K4Fe(CN)6(aq) Cu2Fe(CN)6(s)(Maroon) + 2CH3COO-(aq) + 4K+(aq)

References
http://www.slideshare.net/JessaArio/qualitative-analysis-of-group-4-cations
http://www.wou.edu/las/physci/poston/ch223/GroupII.htm
http://faculty.coloradomtn.edu/jeschofnig/class/class_jeschof/ch2-lb7.htm

 http://chemlab.truman.edu/CHEM131Labs/QualAnalysis.asp
http://pubs.acs.org/doi/abs/10.1021/ed016p77?journalCode=jceda8
http://www.docbrown.info/page13/ChemicalTests/ChemicalTestsc.htm