Qualitative Analysis Lab

Qualitative analysis refers to determining the IDENTITY of an unknown, not the QUANTITY of
the unknown. (That is referred to as Quantitative Analysis!).

In this lab you will analyze solutions containing silver (Ag+), lead (II), (Pb2+) and mercury (I),
(Hg22+) based on their solubility when combined with various anions. At each step you will
identify the ions present in the precipitate as well as the supernatant liquid above the precipitate.

Because chlorides of Ag+, Pb2+ and Hg22+ are insoluble, the first step will be to precipitate the
chlorides from the solution. **Write the net ionic equations for the formation of each solid
chloride.

Because Pb2+ is soluble in warm water, the mixture will be heated to re-dissolve the PbCl2, thus
separating the Pb2+ from the Ag+ and Hg22+.

Addition of potassium chromate to the hot supernatant will precipitate the bright yellow solid,
PbCrO4. **Write the net ionic equation for the formation of solid lead(II) chromate.

AgCl is separated from the Hg2Cl2 by the addition of aqueous NH3. Silver chloride dissolves
because Ag+ forms a soluble complex cation with NH3:

AgCl(s) + 2NH3(aq) → Ag(NH3)2+ (aq) + Cl―(aq)

Mercury (I) chloride reacts with aqueous ammonia in a disproportionation reaction to form a
dark gray precipitate:

Hg2Cl2(s) + 2NH3(aq) → AgNH2Cl(s) + Hg(l) + NH4+(aq) + Cl―(aq)

Although the HgNH2Cl is white, the precipitate appears dark gray because of a colloidal
dispersion of Hg(l)

To verify the presence of Ag+, the supernatant liquid from the last reaction is acidified and AgCl
re-precipitates if Ag+ is present. The acid decomposes the Ag(NH3)2+ by neutralizing the NH3 to
form NH4+. It is necessary that the solution be acidic or else the AgCl will not precipitate and
the Ag+ can be missed.

Ag(NH3)2+(aq) + 2H+(aq) + 2Cl―(aq) → AgCl(s) + 2NH4+(aq)

You will first test a solution that contains all three cations so that you can observe a “positive”
test for each ion. Then you will be given TWO samples containing either one, two or all three of
the cations. Following the same procedure, you will identify the contents of your samples.
Procedure:
Part 1: Precipitation of the Chlorides

Measure out 10 drops of the test solution or the unknown into a small test tube. Add 4 drops of
6M HCl. Stir of shake thoroughly and then centrifuge. Test for completeness of precipitation by
adding 1 drop of 6M HCl to the clear supernate. If the supernate turns cloudy, this shows that
not all the cations have precipitated; add another 2 drops of 6M HCl, stir and centrifuge. Repeat
this process until not more precipitate forms. Decant the supernate into a clean test tube. Wash
the precipitate by adding 5 drops of cold distilled water and stirring. Centrifuge and add the
liquid to the supernate.

Part 2: Separation and Identification of Pb2+

Add 5 drops of distilled water to the precipitate and place the test tube in a hot water bath. Stir
using a stirring rod and heat for 1 minute or longer. Quickly centrifuge and decant the hot
supernate into a clean test tube. Repeat this procedure two more times. Combining the
supernates, which should contain Pb2+ if it is present. Save the precipitate for Part 3. Add 3
drops of 1M K2CrO4 to the supernate. The formation of a yellow precipitate, PbCrO4, confirms
the presence of Pb2+.

Part 3: Separation and Identification of Ag+ and Hg22+

Add 10 drops of 6M NH3 to the precipitate from Part 2. The formation of a dark gray precipitate
indicates the presence of mercury. Centrifuge and decant the clear supernate into a clean test
tube. Add 20 drops 6M HNO3 to the decantate. Stir the solution and test its acidity with litmus
paper. Continue to add HNO3 dropwise until the solution is acidic. A white cloudiness confirms
the presence of Ag+.

DATA:
Record your observations at each stage of the experiment to determine the ions present in your
samples.
Read the procedure on the previous page. Think about what happens during each step of the
procedure. In your lab notebook, design a flow chart to indicate what can be found at each step
of the procedure. Be sure to indicate whether the product is part of the precipitate or the
supernatant. The flow chart below should get you started.

Ag+, Pb2+, Hg22+

Add 6M HCl.

AgCl(s), PbCl2(s), Hg2Cl2(s)

Place in hot water bath

? ?
Supernatant Precipitate