Experiment 4: Qualitative Analysis of Cations and Precipitation Reactions

PURPOSE
Qualitative analysis in inorganic chemistry is concerned with detecting and identifying elements that are present in a
sample of material. In this experiment, you will develop a scheme for the qualitative analysis of three cations, using
a schematic approach. The procedures in the qualitative analysis of this kind involve precipitation reactions to
sequentially remove cations from a mixture of soluble salts. Along each step of the separation, the precipitated
cation will be centrifuged and removed from the remaining soluble cations.

The cations that we will study are Ag+, Pb2+, and Hg22+. The cations will be tested with reagents that will furnish
anions or polyatomic ions that will precipitate the cations. The common test reagents will have a different effect on
the behavior of each of the cations and will provide the basis for their separation. During the first part of this
experiment you will be given a solution that contains all three cations. You will separate the three cations and on the
basis of your observations, you will analyze an unknown solution that contains at least two of the three cations.
Additionally, you will learn the solubility rules to determine the solubility of salts.

OBJECTIVES
In this experiment, you will
1) Develop a scheme for the qualitative analysis of three cations in an aqueous mixture.
2) Use the qualitative scheme to systematically precipitate, separate and identify the three cations in an
aqueous mixture.
3) Use a centrifuge to remove the precipitated ions in from the aqueous solution.
4) Use the qualitative scheme to identify at least two of the three cations in an unknown solution.
5) Learn the basic solubility rules to assess the solubility of salts in aqueous solutions.

CONCEPTS
You should review the following concepts prior to the lab:
1) Naming and identifying salt compounds.
2) Formula unit equation, total ionic equations and net equations for precipitation reactions.
3) Defining qualitative and quantitative analysis.

PRINCIPLES
Solubility of Salts
The solubility of a compound is the amount of the compound that dissolves in a specified volume of water to form
an aqueous solution. Solubility is expressed as either grams/liter or grams/100 mL. Compounds whose solubility in
water is less than 0.1 g/L are usually classified as insoluble compounds. There is no sharp boundary between soluble
and insoluble compounds. Compounds whose solubilities fall near the arbitrary division are called moderately
soluble compounds.

Ionic compounds (salts) that dissolve in water are represented by (aq). In order to determine which of the salts will
dissociate in dilute aqueous solutions, it is necessary to know a few of the solubility rules. Generally, salts composed
of the following ions are completely soluble in dilute aqueous solution. Generally, the ions below are always
spectator ions in reactions that occur in dilute aqueous solutions. These are the rules should know.
i. Group IA metals: Li+, Na+, K+, Rb+, Cs+ and ammonium ion: NH4+
ii. Nitrate ion, perchlorate ion, chlorate ion and acetate ion : NO3−, ClO4−, ClO3− & CH3COO−

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CH204 Experiment 4: Qualitative Analysis of Cations spring 2015

A table of solubility guidelines for common ionic compounds in water is located below in Table 1. However, there
are many exceptions to the solubility rules, especially regarding the slightly soluble compounds. Therefore, you
should know the ones listed above for quiz questions and use the information provided in the table for answering
post-lab questions. Barium sulfate and silver chloride are classic insoluble compounds that are referenced in most
general chemistry texts; therefore, you should recognize those two insoluble compounds as well.

Table 1 Solubility Guidelines for Common Ionic Compounds in Water

Soluble **Slightly soluble Insoluble
Ion
(>10g/L) (0.1 – 10g/L) < 0.1 g/L:

NO3− All

CH3COO− Most AgCH3COO BeCH3COO

*
AgCl, AgBr, AgI,Hg2Cl2,
Cl−, Br−, I− Most PbCl2, PbBr2, HgBr2 Hg2Br2, Hg2I2,
PbI2, HgI2
Group IA metals, AgF, BeF2,
F− Sr2F2, BaF2,PbF2, Most
NH4F

ClO3− All

ClO4− Most

*
These do not dissolve BaSO4, SrSO4, PbSO4,
SO42− Most
well. Mostly solid in Hg2SO4, CaSO4, Ag2SO4
aqueous solution.
Group IA metals, (NH4)2SO3
SO32− Most

Group IA metals, (NH4)2CO3

CO32− Most

Group IA metals, *Ba(OH)2,

NH4OH
OH− *
Sr(OH)2, *Ca(OH)2 Most
These are mostly soluble strong
bases in dilute solutions.
Most (Al3+ and Cr3+ sulfides
2−
S Group I and II metals, (NH4)2S hydrolyze and precipitate as
hydroxides.)
Group IA metals,
PO43− Most
(NH4)3PO4
Group IA metals, BeCrO4, SrCrO4, ZnCrO4, HgCrO4,
CrO42− Most
MgCrO4, CaCrO4 (NH4)2CrO4 NiCrO4, Hg2CrO4
All (except several uncommon
Na+, K+, NH4+
salts)
*Group IA metal hydroxides and the heavier Group IIA metal hydroxides are strong soluble bases in dilute solution.
Barium sulfate and silver chloride are the classic solids in aqueous solution and should be committed to memory.
** Slightly soluble compounds are designated as solids in precipitation reactions.

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CH204 Experiment 4: Qualitative Analysis of Cations spring 2015

Precipitation reactions occur when two compounds dissolved in aqueous solutions react to produce an insoluble
solid. The solid formed may appear as a gel, a suspension (a solid dispersed throughout the solution) or as a solid
that settles to the bottom of the container. The driving force for these types of reactions is the strong attraction
between cations (positive ions) and anions (negative ions) in the solution. The overall result of this type of reaction
is the removal of ions from the solution by the formation of a precipitate (ppt).

When reactions occur in aqueous solution, we can describe the chemical processes by using three kinds of chemical
equations.

a. The formula unit equation shows the balance chemical equation of the reaction and state of all the compounds
that are the reactants and products in the chemical process. E.g. write the formula unit equation for the reaction
when aqueous potassium chromate is added to aqueous lead(II) nitrate to produce yellow solid lead chromate
and aqueous potassium nitrate.

Pb(NO3)2 (aq) + K2CrO4 (aq) → PbCrO4 (s) + 2 KNO3 (aq)

• The symbol (aq) indicates that the ionic compound is dissociated and hydrated in dilute aqueous solution;
that is, it is dissolved in a solution where water is the solvent.
• The symbol (s) indicates that the ionic compound is a solid that is either suspended in or settled out of
solution.

b. The total ionic equation shows the predominant form in which each reactant and product exists when the
reaction occurs in aqueous solution. E.g. write the total ionic equation for the formula unit equation above.

[Pb2+ (aq) + 2 NO3− (aq) ] + [2 K+(aq) + CrO42+ (aq)] → PbCrO4 (s) + 2 K+ (aq) + 2 NO3− aq)

Based on the solubility rules given above, the salts that go through dissolution (dissociate) in aqueous solution are
separated into cations and anions. All ions that are hydrated by water molecules are represented by (aq). The
precipitated salt on the product side is given the symbol (s) indicating that it is a solid compound in solution. Note:
the numbers of ions in a formula unit are represented in the equation by the number preceding the dissociated ions.
There are two nitrate ions in the hydrated formula unit of lead(II) nitrate and two potassium ions in the hydrated
formula unit of potassium chromate; therefore, there are two nitrate ions and two potassium ions represented in the
total ionic equation.

c. The net ionic equation shows the ionic species that react in solution by eliminating the spectator ions from the
total ionic equation. Spectator ions do not react and are ions on both sides of the chemical equation. Essentially,
this equation represents the driving force of the reaction. E.g. write the net ionic equation for the total ionic
equation above.

Pb2+ (aq) + 2 NO3− (aq) + 2 K+(aq) + CrO42+ (aq) → PbCrO4 (s) + 2 K+ (aq) + 2 NO3− aq)
(the spectator ions are removed from the total ionic equation)

Net Ionic Equation (the driving force):

Pb2+ (aq) + CrO42+ (aq) → PbCrO4 (s)

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CH204 Experiment 4: Qualitative Analysis of Cations spring 2015

Qualitative Scheme for Separation of Ions in Solution

Qualitative schemes can be summarized by a flow diagram. For example, a mixture of copper II ions, lead II ions
and tin II ions (Cu2+, Pb2+, and Sn2+) are analyzed.

Step 1. The addition of excess 6 M NaOH will cause the copper II ion to precipitate as Cu(OH)2(s). The lead II
and tin II ions remain in solution as hydroxo-complex ions (Pb(OH)42−(aq) and Sn(OH)42−(aq)). The solid
copper(II) hydroxide is removed by centrifuging.
Step 2. The solution containing the Pb2+ and Sn2+ ions is acidified with 6M H2SO4 causing the lead II ion to
precipitate as PbSO4(s). The solid lead(II) sulfate is removed by centrifuging.
Step 3. The pH of the solution is raised to pH 7 by addition of 6 M NaOH. The addition of 1 M Na2CO3 (aq)
causes the tin II ion to precipitate as SnCO3(s).

The following flow diagram represents a qualitative scheme for the separation of the ions in the example above.

Cu2+, Pb2+, Sn2+

6 M NaOH (step 1)

Cu(OH)2(s) Pb(OH)42− (aq), Sn(OH)42− (aq)

6 M H2SO4 (step 2)

PbSO4 (s) Sn2+ (aq)

6 M NaOH
1 M Na2CO3 (step 3)

SnCO3 (s)

Background for Experimental Procedure:

The chlorides of Ag+, Pb2+, and Hg22+ are insoluble and therefore, they may be precipitated and separated by the
addition of HCl. The following equations represent the reactions that occur:

Pb2+ (aq) + 2Cl– (aq) → PbCl2 (s) white ppt. [1]

Ag+ (aq) + Cl– (aq) → AgCl (s) white ppt. [2]

Hg22+ (aq) + 2Cl– (aq) → Hg2Cl2 (s) white ppt. [3]

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CH204 Experiment 4: Qualitative Analysis of Cations spring 2015

A slight excess of HCl is added to ensure the complete precipitation of the cations. A large excess of added HCl
should be avoided because AgCl and PbCl2 have a tendency to form soluble complexes:

PbCl2 (s) + 2Cl– (aq) → PbCl42– (aq) [4]

AgCl (s) + Cl– (aq) → AgCl2– (aq) [5]

PbCl2 is considerably more soluble than either AgCl or Hg2Cl2. Thus, when PbCl2 precipitates, a significant amount
of Pb2+ remains in solution and can be precipitated with the sulfide ion as PbS. We are only interested in
determining the presence of the Pb2+ ion; therefore, we will not add sulfide ions to the mixture in this experiment.

Lead(II) chloride is much more soluble in hot water than in cold and is separated from the insoluble Hg2Cl2 and
AgCl salts by dissolving it in hot water. The presence of the Pb2+ ion is confirmed by the addition of aqueous
K2CrO4, which forms the insoluble yellow precipitate PbCrO4.

Pb2+(aq) + CrO42− (aq) → PbCrO4 (s) (yellow) [6]

Silver chloride is separated from Hg2Cl2 by the addition of aqueous ammonia (NH3). The silver chloride forms a
soluble complex with the ammonia and dissolves.

AgCl (s) + NH3 (aq) → Ag(NH3)2+ (aq) + Cl− (aq) [7]

Mercury(I) chloride reacts with aqueous ammonia to produce a dark gray precipitate.

Hg2Cl2 (s) + NH3 (aq) → HgNH2Cl (s) + Hg(l) + NH4+ (aq) + Cl− (aq) (dark gray) [8]

Note: the reaction that occurs between mercury(I) chloride and ammonia is called a disproportionation reaction. We
will cover this topic later when we encounter oxidation-reduction reactions. Furthermore, the precipitate, HgNH2Cl,
is actually white; it is the mixture of Hg(l) and HgNH2Cl that gives the precipitate is gray appearance.

Ag(NH3)2+ (aq) + 2 H+ (aq) + Cl− (aq) → AgCl(s) + NH4+ (aq) [9]

To verify the presence of the Ag+ ion, the supernatant containing Ag(NH3)2+ (aq) + Cl− (aq) (from the last reaction)
is acidified. Neutralizing the ammonia in the solution causes the Ag(NH3)2+ to decompose and the Ag+ ion forms a
white AgCl precipitate. It is very important that the solution is acidic at this step or the AgCl will not precipitate and
the Ag+ ion can be missed.

SAFETY
Safety goggles must be worn at all times in the laboratory.
Nitric acid, and hydrochloric acid are corrosive to flesh and can cause severe burns or blindness. In the event of
skin contact, flush the affected area with copious quantities of cold water.
Acetic acid is corrosive to the skin and tissue and a moderately toxic by ingestion and inhalation. It should not be
exposed to open flames.
Potassium chromate may be fatal if swallowed and very harmful if inhaled or absorbed through the skin.
Ammonia is a hazardous chemical is that it is corrosive to the skin, eyes, and lungs. Ammonia has a distinct and
irritating odor when it is released, so your nose is usually the first warning of exposure.

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CH204 Experiment 4: Qualitative Analysis of Cations spring 2015

MATERIALS

Solution mixture that contains 0.1 M AgNO3, 0.20 M Pb(NO3)2, 0.10 M

(3) 310 mm × 75 mm test tubes
Hg2(NO3)2
50 mL beaker 6 M HCl
Bench top centrifuge 6.0 M acetic acid
Wash bottle of distilled water 1.0 M K2CrO4
Hot plate 6 M NH3 (NH4OH)
6 M HNO3

PRE-LAB EXERCISE:
Write a flow diagram in your lab notebook for the separation of the three ions in the procedure below. See example
under Qualitative Scheme for Separation of Ions in Solution.

PROCEDURE
Part 1 – Qualitative Analysis of a Solution of Known Cations (Be sure to record observations in your lab
notebook as you complete the procedure below.)

1. Add enough water to half fill a 250 mL beaker and place on the hot plate. Heat to boiling. This boiling
water will be used to remove the Pb2+ ions in the first separation step. Place a 50 mL beaker on your bench
top to be used as a waste container throughout the experiment.

2. Measure 20 drops (1.00 mL) of the known cation mixture into a small test tube. Add 4 drops of 6 M HCl to
the mixture and swirl to mix thoroughly. Centrifuge the mixture. Be sure there is a counterbalance test
tube in the opposite opening in the centrifuge. A blank test tube with the same volume of water can be
used as a counterbalance.

3. Add 1 more drop of the 6 M HCl to the centrifuged mixture to test for completeness of precipitation. If the
solution is milky, centrifuge again.

4. Decant (carefully pour) the supernatant liquid into a 50 mL waste beaker. The remaining precipitate (ppt)
will be white and contain the solid chlorides of the three cations.
• Decantation is the process separation of a liquid from a solid or sediment by gently pouring the
liquid from the solid without disturbing the solid.
• The supernatant liquid signifies the liquid lying above a solid residue after crystallization,
precipitation or centrifugation.

5. Wash the precipitate with 2 mL of water. (Add the water and thump the test tube softly against your hand to
suspend the precipitate.) Centrifuge again. Decant the supernatant liquid into the waste container.

6. To separate the Pb2+ ions, add 2 mL of distilled water from your wash bottle to the precipitate in the test
tube. Place the test tube in the 250-mL beaker of boiling water for two minutes, swirling occasionally. This
will dissolve most of the PbCl2, but not the other two cations.

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CH204 Experiment 4: Qualitative Analysis of Cations spring 2015

7. Centrifuge the hot mixture. Decant liquid into another test tube in order to test for the Pb2+ ion. Save the
precipitate for further testing.

8. To identify the Pb2+, add one drop of 6.0 M acetic acid and two drops of 1.0 M K2CrO4 to the test tube with
the saved liquid. If the Pb2+ is present, a bright yellow precipitate will form.

9. To separate the Hg22+ ions, add 1.0 mL of 6 M NH3 to the test tube with the saved precipitate and mix –
thump gently on hand. (NOTE: The ammonia is in the bottle labeled NH4OH.)

10. To identify the Hg22+, centrifuge the mixture with ammonia and decant the liquid into a test tube and save.
A gray or black ppt., produced by the reaction of Hg2Cl2 with the ammonia, proves the presence of Hg22+.

11. To identify the Ag+, add about 1 mL 6 M HNO3 to the solution saved in step 10. (The nitric acid is added
to acidify solution.) The Ag+ precipitates in acidic solution. If the white Ag+ ppt. does not appear after the
addition of the nitric acid, add more nitric acid drop wise until the white ppt. appears. Note the volume of
nitric acid needed to ppt. the silver ion for the test of your unknown.)

Part 2 – Qualitative Analysis of a Solution of Unknown Cations

1. Obtain a vial of unknown cations from your TA. Your unknown will be comprised of two or all three of the
cations analyzed above.

2. Follow the above procedure for separation of the solution of known cations to determine your unknowns.

3. Record observations in your lab notebook as you systematically determine your unknowns.

4. Record your unknowns as shown below.

UNKNOWNS: Write the identity of your unknowns.

POST – LAB EXERCISE:

1. A solution sample may contain Ag+, Pb2+, and Hg22+ ions. To determine the presence of any or all of the
ions, 6 M HCl was added to the solution sample and a white precipitate formed. The precipitate was heated
in hot water, centrifuged and the supernatant was decanted. No precipitate formed when acetic acid and
potassium chromate were added to the supernatant. When 6 M NH3 was added to the remaining white
precipitate the solid dissolved but no precipitate was formed. Answer the following questions based on the
information provided above.
a. Which of the three possible ions are absent in the solution sample? How do you know?
b. Which of the three possible ions are present in the solution sample? How do you know?

2. Determine if the following reactions will form a precipitate when solutions of the reactants are mixed. If a
precipitate is formed when the reactants are mixed, write the balanced formula unit, the complete ionic and
the net ionic equations for the reactions. If a precipitate does not form when the reactants are mixed, write

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CH204 Experiment 4: Qualitative Analysis of Cations spring 2015

NR (no reaction) to the right of the arrow. Do not forget to include the physical states of the reactants and
products; (aq), (s), (l), (g) in your three solution equations.
a. Fe(NO3)2 (aq) + K3PO4 (aq) →
b. Ba(OH)2 (aq) + Pb(ClO3)2 (aq) →
c. Al(ClO4)3 (aq) + Na2SO3 (aq) →
d. CaCl2 (aq) + (NH4)2SO4 (aq) →
e. LiCH3COO (aq) + MgCl2 (aq) →

DISCUSSION (Attach written discussion to end of lab report.) 50 points

1. What were the objectives of this experiment?

2. Why was it necessary to add HCl to the mixture of cations at the beginning of the separation process? Why
was it necessary to avoid adding too much HCl during this first step? After the HCl was added to the
mixture, the mixture was centrifuged and another drop HCl was added. Why?
3. How was the lead(II) ion separated from the sample solution mixture? How was the presence of the
lead(II) ion tested? Was the lead(II) ion present or not present in your unknown?
4. How was the mercury(I) ion separated from the sample solution mixture? How was the presence of the
mercury(I) ion tested? Was the mercury(I) ion present or not present in your unknown?
5. How were the silver ions separated from the sample solution mixture? How was the presence of the silver
ions tested? Was the silver ion present or not present in your unknown?
6. Discuss any difficulties you may have had with the experiment and suggest possible ways in which you
could improve your experimental outcome.

Be sure to upload a copy of your discussion into SafeAssign before your next lab period.

References:
Zumdahl, S. S. Chemical Principles, 5th Edition, Houghton Miffin Company, 2005, pp. 107, 329-330, 98-99, 104-
106.
Atkins, P.W.; Jones, L. L. Chemical Principles: The Quest for Insight, 3rd Edition, W. H. Freeman and Company,
2005, pp. F4, F51, 431-432.

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