CHY 33.

1 Qualitative Chemistry Laboratory

Activity #4 Group 1 Cations

INTRODUCTION
The qualitative analysis of certain metal cations can be carried out successfully by
applying the principles of solubility rules and understanding the concepts of ionic equilibrium,
acids and bases reactions, pH, oxidation and reduction reactions, and complex formations.
The grouping of metal ions is based on their selectivity to specific reagents that allow for
their separation from a mixture. This process of separating a group of cations or a particular
cation using a specific reagent is called selective precipitation.
Using selective precipitation reactions, cations are sequentially removed from a mixture.
If the precipitate can contain only one cation under the prevailing conditions, that precipitate
serves to prove the presence of that cation, a confirmatory step. If the precipitate may contain
several cations, it can be dissolved and further separated in a series of steps that may include
acid-base, complex ion formation, redox, or other precipitation reactions. The ultimate result is
separating the mixture into fractions that can contain only one cation, whose presence is
established by forming a characteristic precipitate or a colored complex ion.
Group 1 is among common metal ions but are the only ones that form insoluble chlorides
with HCl, while the other cations, if present, remain in solution. Many ions have similar chemical
properties, but each ion has a unique property that can be used to characteristically identify it in
a mixture. However, the interferences of ions with similar properties must be eliminated first. In
this activity, the characteristic reactions of the Group 1 cations, namely, Ag+, Hg22+, and Pb2+, will
be explored.

OBJECTIVES
By the end of the experiment, the student should be able to:
1. Perform the systematic qualitative process for analysis of group 1 cations, and
2. Construct and utilize an analysis flow diagram for the qualitative separation and identification
of Group 1 cations.

SAFETY PRECAUTIONS
Several reagents, such as strong acids, bases, corrosives, and even toxic chemicals, are
included in this experiment. The use of gloves is required for conducting the experiment, while
the use of goggles or safety glasses is highly recommended. You are expected to have read and
understood the procedure before beginning the experiment. Ask questions if there is anything
unclear in the procedure.
PROCEDURE
Step 1. Separation of Group 1 cations from a mixture
Qualitative analysis of metal cations begins with separation by precipitation of the group
1 cations. In this experiment, the positive control is a solution of equal volumes of 0.1M AgNO 3,
0.2M Pb(NO3)2, and 0.1M Hg2(NO3)2.
Add 2 drops of 6M HCl to 1 mL of the sample solution. Mix with a stirring rod. Centrifuge
the mixture. (The proper use of centrifuge will be demonstrated. Do not proceed unless you have
learned the equipment operation.) Check for completeness of precipitation by adding one more
drop of 6M HCl to the centrifuged mixture. Decant the supernatant, which should contain other
cations groups if present, into another test tube and save.
Step 2. Separation of Pb2+
Wash the precipitate from Step 1 by adding 1 to 2 mL water, stir, centrifuge and decan
the supernatant. This liquid can be discarded. Add 2 mL of distilled water to the washed
precipitate and place the tube in a boiling water bath. Leave this for 1-2 minutes with occasional
stirring. Centrifuge the hot mixture and decant the supernatant to a new test tube. This will
contain the dissolved Pb2+ ions. Save the residue for further testing.
Step 3. Confirmatory test for Pb2+
To the liquid in Step 2, add 1 drop of 6M Acetic acid (HC 2H3O2) and a 3-5 drops of 0.1M
K2CrO4. A bright yellow precipitate of PbCrO 4 will form to confirm the presence of Pb 2+.
Step 4. Separation and Confirmatory test for Hg22+
Add 1 mL of 6M NH3 to the precipitate in Step 2 and stir thoroughly. A gray to black
precipitate forms from the reaction of Hg22+ with NH3 will form. Centrifuge the mixture and
decant the liquid into a new test tube.
Step 5. Confirmatory test for Ag+
Add dropwise 6M HNO3 to the solution in Step 4 until the solution is acidic by litmus test.
If the solution is sufficiently acidic, Ag+ will form a white precipitate for AgCl. AgCl is insoluble in
an acidic medium and this is a characteristic property of the solid used for its separation.

RECORD ALL OBSERVATIONS IN THE WORKSHEET

PRELAB QUESTION/s
A flow diagram is often used to organize the sequence of test procedures for separating and
identifying a large number of ions in a mixture. Based on the given procedure for this exercise,
complete the flow diagram for the analysis of Group 1 cations below.

Reference:

Slowinski E., Wolsey W., and Rossi, R., Chemical Principles in the Laboratory, 2011. Brooks/Cole
CENGAGE Learning, USA
 ACTIVITY #3 TEST FOR COMMON ANIONS
WORKSHEET
Group Name/#: ____________________ Section: ________________________
Members: _________________________
_________________________
_________________________
_________________________
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FLOW DIAGRAM. Draw a flow diagram of the Group 1 Cations Analysis. Indicate actual
observations if different from expected. Write observations of positive control in black ink. Write
your unknown sample observations in colored ink (not black).
Questions:

1. Write balanced net ionic equations for the following reactions:

a. The precipitation of the chloride of Hg22+

b. The dissolving of PbCl2 in hot water.

c. The dissolving of AgCl in aqueous ammonia

2. A solution may contain Ag+, Pb2+, and Hg22+. A white precipitate forms on addition of 6 M HCl.
The precipitate is insoluble in hot water. The residue turns black on addition of ammonia. Which
of the ions are present, which are absent, and which remain undetermined? State your
reasoning. Note: On paper unknowns such as this one, confirmatory tests are usually not
included.
Present ____________ Absent ____________ In doubt ____________