THE SILVER GROUP

Stephanie M. Westhuis
Lab # 6
March 26, 2011

THE SILVER GROUP

Introduction

The “silver group” consists of the following ions: Ag+, Pb+, and Hg22+.
These cations are the only three of the common metal ions that form
insoluble chlorides. They are also insoluble in cold, dilute hydrochloric
acid. These attributes form the basis for the separation of these silver-
group cations from all other metallic cations. The process used to
achieve this separation is called precipitation. Precipitation is a form of
qualitative analysis in which an insoluble substance forms in, and
separates from, a solution. In this experiment, precipitation was used
to detect and remove the Ag+, Pb+, and Hg22+ ions from a solution by
precipitating them as AgCl, PbCl2, and Hg2Cl2 using a known sample
and an unknown sample numbered “02.”

Procedure 1:

Procedure 1 was used to precipitate the silver group from the other
metallic cations.
• Five (5) drops of the unknown solution to be analyzed was
placed in a 3-in.
test tube along with 5 drops of water.
• Two (2) drops of 6M HCl was added and mixed thoroughly with
a glass stirring
rod.
• A few drops of cold water was used to wash down the test tube
to flush any
adhering precipitate back into the solution.
• The solution was centrifuged and then tested for complete
precipitation by adding another drop of 6M HCl to the clear
supernatant solution in the test tube.
• When precipitation was complete, the solution was centrifuged
again and decanted.
• The precipitate was washed with five (5) drops of cold water,
decanted, and allowed to remain in the test tube for analysis
according to Procedure 2.

The above steps were simultaneously performed using the known

sample.

Results:

A white precipitate was formed in both test tubes which indicated the
presence of silver group ions. The white precipitate at that point was a
mixture of AgCl, PbCl2, and/or Hg2Cl2.
Procedure 2:

Procedure 2 was used to separate lead ions from mercury (I) and silver
ions.

• Fifteen (15) drops of hot water was added to the test tube
containing the precipitate from Procedure 1 and stirred well until
all the precipitate was in suspension.
• The test tube was then heated by placing it in a 100-mL beaker
of boiling water for approximately one (1) minute and stirred
frequently.
• The test tube was centrifuged immediately and decanted into
another test tube. The decantate, which contained the Pb2+ was
saved for Procedure 3.
• The precipitate was washed twice with 10-drop portions of hot
water and saved in the test tube for Procedure 4.

The above steps were simultaneously performed using the known

sample.
.
Results:

Since PbCl2 is soluble in hot water, and AgCl, and Hg2Cl2 are insoluble,
this part of the experiment was able to separate the lead from the mercury
(I) and silver ions. Boiling water was used because a much larger amount of
PbCl2 could be dissolved than water at room temperature.

Procedure 3:

Procedure 3 was used to detect and confirm the presence of lead.

• The decantate from Procedure 2 was cooled and divided into
two parts.
• One (1) drop of 0.2M K2CrO4 was added to the first part and
one (1) drop of
2M H2SO4 was added to the second part.

The above steps were simultaneously performed using the known

sample.

Results:

The addition of 0.2M K2CrO4 proved the presence of lead by creating a

yellow precipitate in the first test tube. The insertion of 2M H2SO4 into the
second test tube slowly formed a white precipitate which was further
confirmation of the presence of lead in the sample. The known sample
provided identical results.

Procedure 4:

Procedure 4 was used to separate and detect mercury (I) and silver.
• Four (4) drops of 15M aqueous NH3 was added to the
precipitate that was
saved from Procedure 2.
• The contents were mixed thoroughly, centrifuged and decant
into another test
tube. The decantate was saved for testing the silver.
• To the decantate, 16M HNO3 was added drop by drop and
mixed constantly
with a stirring rod until slightly acidic.
• Litmus paper was placed on a clean towel to test for the
acidity of the solution
and the stirring rod was withdrawn from the solution and
touched to the litmus
paper.

The above steps were simultaneously performed using the known

sample.

Results:

The addition of 15M aqueous NH3 to the test tube from Procedure 2
resulted in a grayish-black residue which indicated the presence of mercury
(I). The addition of 16M HNO3 to the decantate formed a white precipitate
(AgCl) and proved the presence of silver. The known sample produced the
same results.

Overall Results:

In Procedure 1, Ag+, Pb+, and Hg22+ were removed as a group from

solution by the addition of HCl. The reactions that occurred were simple
precipitations represented by the equations:
Pb2+ (aq) + 2Cl- (aq) → PbCl2 (s)
Ag+ (aq) + Cl- (aq) → AgCl (s)
Hg22+ (aq) + 2Cl- (aq) → Hg2Cl2 (s)

In Procedure 2, PbCl2 was separated from the AgCl and Hg2Cl2 by

dissolving the lead chloride in hot water, stirring, boiling, and then
centrifuging.
 In Procedure 3, lead was detected in both the known and unknown
solution samples using two tests. In the first test, 0.2M K2CrO4 was added.
A yellow precipitate of PbCrO4 confirmed the presence of lead. In the second
test, 2M H2SO4 was added which secondarily confirmed lead’s presence by
revealing a white precipitate. Those reactions are shown in the equations
below.
Pb2+ + CrO42-  PbCrO4
Pb2+ + H2SO42-  PbSO4

In Procedure 4, mercury (I) and silver were separated detected in both

the known and unknown solution samples. Mercury (I) was found as a
grayish-black residue with the addition of 15M aqueous NH3 to the
precipitate from Procedure 2. The decantate was preserved and 16M HNO3
added which indicated the presence of silver with the formation of a white
precipitate. Those reactions are represented by these two equations:

Hg2Cl2+ + 2NH3  HgNH2Cl + NH4+ Cl-

Ag+ + 2NH3  Ag(NH3)2+

The complete process and overall scheme of analysis of the silver group in
this experiment is illustrated below:
One significant error was made during the course of this experiment.
The experimenter’s original unknown sample was numbered “700.”
However, after confirming the presence of lead in the sample, it was
accidentally deposited in the sink. The experimenter continued the
laboratory exercise with a fellow classmate using sample “02,” the results of
which are described in this report. It is possible that other small errors
occurred, although if that is the case, they weren’t considerable as the
outcomes of each stage of the experiment were incontrovertible.

Conclusion:

In this experiment, a known solution that contained silver, lead, and

mercury (I) and an unknown solution were qualitatively analyzed to
determine which ions were present and which were absent. Both the known
and the unknown were found to contain Ag+, Hg22+ and Pb2+ ions based on
the procedures and outcomes heretofore described.

References:

Brown, T.L, et al., (2009). Chemistry: The Central Science (11th ed.). New
Jersey: Prentice-Hall.
Wismer, R.K. (1991). Qualitative Analysis and Ionic Equilibrium. Retrieved on
3-24-2011 from

http://classes.uleth.ca/200801/chem20001/1237%20Expt1_Qual2008.pdf.