ANALYSIS OF GROUP I CATIONS 1

OBJECTIVES:

When this experiment is completed you should be able to:

✓ Further develop the laboratory technique of “flowcharting”.

✓ Be able to write balanced equations for the confirmatory tests of the Group I Cations.

✓ Demonstrate an understanding of the basic techniques of centrifuging and decantation by

performing the Group I Analysis of a known sample.

PRELAB PREPARATION:

1. Read the lab discussion and procedures to decide (and write down) your learning objective.

2. Summarize the discussion in bullet format.

3. Flowchart the procedures (on a new page). Don’t forget to watch for places to make observations
and make measurements.

4. Prepare an observations table and a data table (on a new page). Leave space for “unexpected”
observations (in addition to the ones you’re looking for).

DISCUSSION:

Kotz (textbook) references: Chapter 17, Section 17-5 and 17-7.

There are three cations in Group I; Ag+1, Pb+2, Hg2+2. These cations form insoluble chlorides and
can be separated from the cations of Groups II and III using this property. In their elemental form, all
are classified as metals; however, they form partial covalent bonds with many anions due primarily to
the small electronegativity difference between these metals and their combining anions.

Silver has an electron configuration [Kr] 5s1 4d10. Its singular “s” electron gives it a common
oxidation number of +1. Lead has an electron configuration of [Xe] 4f14 5d10 6s2 6p2. It exhibits two
oxidation numbers; +2 and +4, with the +2 state being the most common. The electron configuration of
mercury is [Xe] 6s2. The first ionization energy of mercury is very high when compared to other metals
such as silver and gold. The resulting Hg+1 ion is very unstable and exists as the dimer ( Hg 22 )
(Hg+1-Hg+1). This dimer has a tendency to undergo auto-oxidation and favors the formation of the Hg+2
ion in the presence of certain anions.

( Hg 22 )(aq) ⇌ Hg 0 (l) + Hg 2 (aq) [1]

Copyright 2008, Daytona State College, Department of Biological and Physical Sciences, May not be reproduced or altered
without permission from the authors. For information, email endebrk@daytonastate.edu. Revised: 1/12/2018
 ANALYSIS OF GROUP I CATIONS 2

PROCEDURE: Obtain a known ion sample. Using only your flow chart, go through the
Group I/Group II separation, then the Group I ion analysis. Be sure to note the colors of the compounds
used in the confirmatory tests in your observations table along with anything else you find important.

Turn your data and observations tables in to your instructor before you leave the lab.

BLOCK OUTLINE Analysis of Group I Cations

Solution contains the following ions from Groups I and II: Ag+1, Hg2+2, Pb+2, Bi+2, Cu+2, Cd+2, Sn+4,
Hg+2. You will be separating these two groups for study in this lab and the next one.
Add 15-20 drops of the solution to a clean microcentrifuge tube and dilute to 1 mL with distilled water.
Add 2 drops of 6M HCl (NOTE 1). Stir thoroughly and cool in an ice bath. Centrifuge and decant.

DECANTATE: Cations of Group II Group I PRECIPITATE: AgCl, Hg2Cl2, PbCl2

SAVE THIS SOLUTION! It In a separate microcentrifuge tube, prepare a wash of 2 mL
contains your Group II Known (or distilled water with 1 drop 6M HCl (NOTE 2); chill in ice bath
Unknown) Cations! Wash the precipitate with 10 drops of wash. Centrifuge and
decant.

DECANTATE: Add to Cations Group I PRECIPITATE: AgCl, Hg2Cl2, PbCl2

of Group II. SAVE THIS Wash the precipitate a second time with 10 drops of wash.
SOLUTION! Centrifuge and decant.

DECANTATE: Discard Group I PRECIPITATE: AgCl, Hg2Cl2, PbCl2

Add 20 drops HOT distilled water; heat in water bath for
2 minutes (NOTE 3). Centrifuge and decant while warm.

PRECIPITATE: AgCl, Hg2Cl2, DECANTATE: Pb+2

Add 10 drops 4M NH3. Centrifuge and Add 2 drops 1M K2CrO4
decant. Yellow precipitate (PbCrO4) confirms the
presence of Pb+2

PRECIPITATE: DECANTATE:
Black (Hg(l)) and white (HgNH2Cl), Adjust the pH to 4-5 with 4M HNO3.
or Gray (mixture of the above) White precipitate (AgCl) confirms the
confirms the presence of Hg2+2 presence of Ag+

Copyright 2008, Daytona State College, Department of Biological and Physical Sciences, May not be reproduced or altered
without permission from the authors. For information, email endebrk@daytonastate.edu. Revised: 1/12/2018
 ANALYSIS OF GROUP I CATIONS 3

NOTES ON THE ANALYSIS OF GROUP I CATIONS

1. A large excess of chloride ions (from the addition of too much HCl) can re-dissolve precipitates
of silver and lead, converting them to soluble complex ions as shown below.

AgCl(s) +2 Cl(aq) ⇌ AgCl32- (aq)

PbCl2(s) + Cl(aq) ⇌ PbCl24- (aq)

2. Lead (II) chloride may dissolve appreciably in the washing process; consequently, the wash
water should contain a small quantity of chloride ions (from HCl) so that the solubility of lead is
reduced by the common ion effect.

3. Lead (II) chloride is fairly soluble in hot water but may re-precipitate if the solution is allowed to
cool. Failure to keep the solution hot may result in a weak or confusing test for lead.

POST-LAB DATA ANALYSIS:

Assemble your postlab report; no title page is required. For each confirmatory precipitate
(PbCrO4, AgCl, HgNH2Cl, Hg), write a net ionic equation and note colors of products.

Write a conclusion that addresses your learning objective and observations. What did you learn
in the lab? What did you do “right” or “wrong;” how can you avoid making the same mistakes? How
can you improve your lab techniques? How can you improve your flowchart?

REACTIONS OF THE GROUP I CATIONS

LEAD: Pb2+(aq) + 2 Cl(aq)  PbCl2(s)

(white)
PbCl2(s) + Hot Water  Pb2+(aq) + 2 Cl(aq)
Pb2+(aq) + CrO24- (aq)  PbCrO4(s)
(yellow)
SILVER: Ag+(aq) + Cl(aq)  AgCl(s)
(white)
AgCl(s) + 2 NH3(aq)  Ag(NH 3 ) 2 (aq) + Cl(aq)

Ag(NH 3 ) 2 (aq) + Cl(aq) 2 H3O+(aq)  AgCl(s) + 2 NH 4 (aq) + 2 H2O(l)

(white)

MERCURY: Hg 22 (aq) + 2 Cl(aq)  Hg2Cl2(s)

(white)
Hg2Cl2(s) + 2 NH3(aq)  HgNH2Cl(s) + Hg(l) + NH 4 (aq) + Cl(aq)
(white) (black)

Copyright 2008, Daytona State College, Department of Biological and Physical Sciences, May not be reproduced or altered
without permission from the authors. For information, email endebrk@daytonastate.edu. Revised: 1/12/2018