I.

Introduction
Qualitative analysis is a branch of analytical chemistry that deals with the separation and
identification of the components of matter - what is present, not how much is present. There are
many common qualitative analysis schemes that separate the ions into groups based on selective
precipitation. Although sophisticated instrumental techniques have replaced much of the
traditional wet chemistry analytical methods, qualitative analysis remains an important part of
the laboratory experience in general chemistry.
In qualitative analysis, the ions in a mixture are separated by selective precipitation.
Selective precipitation involves the addition of a carefully selected reagent to an aqueous mixture
of ions, resulting in the precipitation of one or more of the ions, while leaving the rest in
solution. Once each ion is isolated, its identity can be confirmed by using a chemical reaction
specific to that ion.
It is important to learn this analysis in order to know the ions involved in an unknown
sample. It helps to solve some environmental problems such as contamination of unknown ions
in a body of water, contamination of a toxic chemical in foods, etc.

II.

Objective
The objective of this laboratory was to follow a classic analytical scheme to separate and
identify the ions in a known mixture of Group 1 cations, and then to then apply this scheme
to identify the ions in an unknown mixture of Group 1 cations.

III.

Materials
The needed materials were 8 small test tubes, glass stirring rod, small 10-mL graduated cylinder,
250-mL beaker, dropper, blue litmus paper, wash bottle filled with deionized water, hot plate, and
centrifuge.

IV.

Procedure
Step 1. To 3 mL of the sample in a test tube, we added 0.5 mL 6 M HCl. Then, stirred well and
centrifuged. The group decanted the liquid, which may contain ions from other cation groups, into a
test tube and saved it, if necessary, for further analysis; to make sure precipitation of Group I cations
was complete, we added one drop of 6 M HCl to the liquid. We washed the precipitate with 2 mL
water and three drops of 6 M HCl. Then, we stirred it well. The group centrifuged the sample and
discarded the wash liquid. Next, we washed the precipitate again with water and HCl; centrifuged
and discarded the wash.
Step 2. To the precipitate from Step 1, which contains the chlorides of the Group I cations was
added about 5 mL water. Then, the sample was heated in the boiling water bath for at least 3
minutes, stirring constantly. The sample was centrifuged quickly and decanted the liquid, which may
contain Pb2+, into a test tube.
Step 3. Confirmation of the Presence of Lead.
To the liquid from Step 2, the group added two drops of 6 M acetic acid and three or four
drops of 0.5 M K2CrO4 . The formation of a yellow precipitate of PbCrO4 confirmed the presence of
lead. Centrifuging out the solid may help with the identification, because the liquid phase is orange.
Step 4. Confirmation of the Presence of Mercury.
If lead was present, we washed the precipitate from Step 2 with 6 mL water in the boiling
water bath. Then, centrifuged and tested the liquid for Pb2+. We continued the washings until no

positive reaction to the lead test was obtained. To the washed precipitate, we added 2 mL 6 M
NH3 and stirred well. A black or dark gray precipitate established the presence of the mercury(I)
ion. We centrifuged and decanted the liquid, which may contain Ag(NH3 )2+, into a test tube. \
Step 5. Confirmation of the Presence of Silver.
To the liquid from Step 4, the group added 3 mL 6 M HNO3 . We checked with litmus to see
that the solution was acidic. A white precipitate of AgCl confirmed the presence of silver.
Step 6. Alternative Confirmation of the Presence of Silver.
If the test for silver ion was inconclusive, and mercury was present, we went back to the
precipitate from Step 4. We washed the precipitate with 3 mL of water, centrifuged, and
discarded the liquid. To the precipitate, we added 1 mL 6 M HCl and 1 mL 6 M HNO3 , and put
the test tube in the water bath. Within a minute or two all of the mercury-containing species
would dissolve, leaving, if silver was present, a curdy, bluish-gray precipitate of AgCl. We
centrifuged out the precipitate, and carefully decanted the liquid, making sure not to decant the
solid. We washed the solid with 2 mL water, centrifuged, and discarded the wash. To the solid,
we added 1 mL 6 M NH3 ; with stirring, the precipitate should dissolve. Then, we added 6 M
HNO3 until the solution was acidic. If silver was present, a white precipitate of AgCl would
form.
V.

Data and Observations

A. Group I Flow Chart

B. Chemical equations of each reaction

Confirmation of Pb2+

a.) Dissolution of Lead(II) cation in hot water.

PbCl 2 (s) Pb2+ (aq) + 2Cl (aq)
b.) Addition of K2CrO4 to the cation.
Pb2+(aq) + K2Cro4(aq) PbCrO4(s) + K+(aq)
c.) Addition of K2CrO4 to the reprecitated AgCl.
PbCl2(aq) + K2CrO4(aq) PbCrO4(s) + KCl(aq)

Confirmation of Ag+
a.) AgCl and Hg2Cl2, can be separated by adding aqueous
ammonia.
AgCl(s) + 2NH3 (aq) Ag(NH3 )2 + (aq) + Cl (aq)
b.) The addition of a strong acid (HNO3) to the
solution destroyed the complex ion and
reprecipitated silver chloride.
Ag(NH3 )2 + (aq) + 2H+ (aq) Ag+ (aq) + 2NH4 + (aq)
Ag+ (aq) + Cl (aq) AgCl(s)
Ag(NH3 )2 + (aq) + 2H+ (aq) + Cl (aq) AgCl(s) + 2NH4 + (aq)
white

Confirmation of Hg22+
a.) Ammonia also reacted with Hg2Cl2 via a rather unusual
oxidation-reduction reaction. The products included finely
divided metallic mercury, which was black, and a compound
of formula HgNH2Cl, which was white:
Hg2Cl 2 (s) + 2NH3 (aq) Hg (l) + HgNH2Cl(s) + NH4 + (aq) + Cl (aq)
white

VI.

black

white

Results and Discussion

In the classical qualitative analysis scheme, Ag+ , Pb2+, and Hg2 2+ comprised Group I in the scheme
and were separated from a general salt solution by precipitation of their chlorides at a pH of about zero. This
allowed the removal Ag+ , Pb2+, and Hg2 2+ as a group from solution by the addition of HCl. The reactions
that occurred were simple precipitations and could be represented by the equations:

Ag+ (aq) + Cl (aq) AgCl(s)

(1)

Pb2+ (aq) + 2Cl (aq) PbCl 2 (s)

Hg2 2+ (aq) + 2Cl (aq) Hg2Cl 2 (s)

(2)
(3)

For the confirmation of Pb2+ , which was soluble in hot water because the Ksp of PbCl2 greatly
increased with temperature favoring less solid and more ions, cooling of the sample resulted to the
reprecipitation of Pb2+ as PbCl2. The addition of K2CrO4 showed the presence of the Lead(II) by the yellow
precipitate which was PbCrO4.
PbCl2(aq) + K2CrO4(aq) PbCrO4(s) + KCl(aq)
The precipitate in the unknown sample contained the two insoluble chlorides, Ag+ and Hg22+. The
two cations can be separated by the addition of aqueous ammonia. Silver cation formed a complex ion
Ag(NH3)2+.
AgCl(s) + 2NH3 (aq) Ag(NH3 )2 + (aq) + Cl (aq)
On the other hand, Hg22+ by a oxidation-reduction reaction, formed a metallic mercury, which was
black and a compound (HgNH2Cl), which was white.
Hg2Cl 2 (s) + 2NH3 (aq) Hg (l) + HgNH2Cl(s) + NH4 + (aq) + Cl (aq)
As this reaction occurred, the solid appeared to change color, from white to black or grey.
The presence of Ag+ was further tested by the addition of a strong acid HNO3. This destroyed the
complex ion and reprecipitated AgCl.
Ag(NH3 )2 + (aq) + 2H+ (aq) + Cl (aq) AgCl(s) + 2NH4 + (aq)
In the experiment, the group had only confirmed the presence of silver cation as a practice for the
qualitative analysis of unknown cations. We used the chemical Ag2SO4 as the sample of the confirmation.
We added 6M HCl to the sample. It was important to add enough HCl to ensure complete precipitation, but
too large an excess. In concentrated HCl solution, these chlorides would tend to dissolve, producing chlorocomplexes such as AgCl2 - . The reaction below showed the presence of silver cation.
Ag2SO4 (aq) + HCl(aq) AgCl(s) + H2SO4 (aq)
VII.

Conclusion
By the different solubilities of the cations, we can separate the cations and confirmed by the use
of compound that can specify the kind of cation that is being involved in the unknown sample.
Selective precipitation is an important thing in the qualitative analysis. It helps to identify the cations
in the unknown sample and separate the ion to the other group of ions.

VIII.

Reference/ Retrieved from:

http://home.comcast.net/~christylthomas/apqual.pdf