Confirmatory tests for Fe2+, Fe3+, Pb2+ 

and NH4+ ions
Ammonium ion, NH4+

Method I: Heating an ammonium salt with a strong alkali

(a) Procedure:
(i) About 2 cm3 of ammonium chloride solution is poured into a test tube.
(ii) About 4 cm3 of dilute sodium hydroxide solution is added to the test tube and the mixture is shaken well.
(iii) The mixture is carefully heated and the gas liberated is tested with a piece of moist red litmus paper.
(b) Observation:
The colourless gas evolved turns red litmus paper blue.

(c) Explanation:
Heating an ammonium salt with an alkali produces ammonia gas.
NH4+(aq) + OH–(aq) → NH3(g) + H2O(l)
The alkaline ammonia gas turns red litmus paper blue.

Method II: Reacting with Nessler’s reagent

(a) Procedure:
(i) About 2 cm3 of ammonium chloride solution is poured into a test tube.
(ii) A dropper is used to add Nessler’s reagent drop by drop to the solution.
(iii) Any change that occurs is noted.
(b) Observation:
A brown precipitate is formed.
(c) Explanation:
Ammonium ion reacts with a complex ion in Nessler’s reagent to produce a brown precipitate.

Iron(II) ion, Fe2+

(a) Procedure:
(i) About 2 cm3 of iron(II) sulphate solution is poured into a test tube.
(ii) A dropper is used to add potassium hexacyanoferrate(III), K3Fe(CN)6 solution, drop by drop into the test tube.
(iii) Any change that occurs is recorded.
(b) Observation:
A dark blue precipitate is obtained.
(c) Explanation:
The iron(II) ion combines with a complex ion in the reagent to produce a dark blue precipitate.
Fe2+(aq) + Fe(CN)63-(aq) → dark blue precipitate

Iron(III) ion, Fe3+

Method I: Reacting with potassium hexacyanoferrate(II), K4Fe(CN)6 solution

(a) Procedure:
(i) About 2 cm3 of iron(III) chloride solution is poured into a test tube.
(ii) A dropper is used to add potassium hexacyanoferrate(II) solution drop by drop into the test tube.
(iii) Any change that occurs is noted.
(b) Observation:
A dark blue precipitate is formed.
(c) Explanation:
The iron(III) ion combines with a complex ion in the reagent to produce a dark blue precipitate.
Fe3+(aq) + Fe(CN)64+(aq) → dark blue precipitate

Method II: Reacting with potassium thiocyanate, KSCN solution

(a) Procedure:
(i) About 2 cm3 of iron(III) chloride solution is poured into a test tube.
(ii) A dropper is used to add potassium thiocyanate solution drop by drop into the test tube.
(iii) Any change that occurs is recorded.
(b) Observation:
A blood-red colouration is seen.
(c) Explanation:
The thiocyanate ion from potassium thiocyanate combines with iron(III) ion to form a blood-red colouration.
Fe3+(aq) + SCN–(aq) → FeSCN2+(aq) (blood red)

Lead(II) ion, Pb2+

Method I: Reacting with sodium chloride

(a) Procedure:
(i) About 2 cm3 of lead(II) nitrate solution is poured into a test tube.
(ii) A dropper is used to add about 1 cm3 of sodium chloride solution into the test tube.
(iii) About 3 cm3 of distilled water is added and the mixture is boiled.
(iv) The mixture is then cooled using running water from the tap.
(v) Any change that occurs is recorded.
(b) Observation:
A white precipitate which dissolves in hot water and reappears when cooled is formed.
(c) Explanation:
Chloride ion from sodium chloride combines with lead(II) ion to form a white precipitate of lead(II) chloride.
Pb2+(aq) + 2Cl–(aq) → PbCl2(s)
The precipitate is insoluble in cold water but dissolves in hot water.

Method II: Reacting with potassium iodide

(a) Procedure:
(i) About 2 cm3 of lead(II) nitrate solution is poured into a test tube.
(ii) A dropper is used to add about 1 cm3 of potassium iodide solution into the test tube.
(iii) About 3 cm3 of distilled water is added and the mixture is boiled.
(iv) The mixture is then cooled using running water from the tap.
(v) Any change that occurs is recorded.
(b) Observation:
A yellow precipitate which dissolves in hot water is formed.
On cooling, golden yellow crystals are formed.
(c) Explanation:
Iodide ion from potassium iodide combines with lead(II) ion to form a yellow precipitate of lead(II) iodide.
Pb2+(aq) + 2I–(aq) → PbI2(s)
The precipitate is insoluble in cold water but dissolves in hot water.

Cation Sodium hydroxide solution Ammonia solution Other reagent

NH4+ Ammonia gas evolved when Nessler’s reagent: brown

–
mixture is heated. precipitate

White precipitate. Insoluble in White precipitate. Insoluble in

Mg2+ –
excess alkali. excess alkali.

White precipitate. Insoluble in Concentrated H2SO4: white

Ca2+ No precipitate.
excess alkali. precipitate

White precipitate. Kl(aq): yellow precipitate

White precipitate. Insoluble in
Pb2+ Soluble in excess alkali to form NaCl(aq): white precipitate
excess alkali.
colourless solution. Na2S04(aq): white precipitate
 White precipitate.
White precipitate. Insoluble in
Al3+ Soluble in excess alkali to form –
excess alkali.
colourless solution.

White precipitate. White precipitate.

Zn2+ Soluble in excess alkali to form Soluble in excess alkali to –

colourless solution. form colourless solution.

K3Fe(CN)6: dark blue precipitate

Green precipitate. Insoluble in Green precipitate. Insoluble in
Fe2+ KMn04: purple colour of the
excess alkali. excess alkali.
solution is decolourised

K4Fe(CN)K6: dark blue

Brown precipitate. Insoluble in Brown precipitate. Insoluble in
Fe3+ precipitate
excess alkali. excess alkali.
KSCN: blood-red colouration

Blue precipitate.
Blue precipitate.
Cu2+ Soluble in excess alkali to –
Insoluble in excess alkali.
form dark blue solution.

Identifying the anions and cations in unknown salts

1. Use the knowledge you have- learnt about the reactions of anions and cations to help you plan and carry out
experiments to identify the anions and cations in an unknown salt.
2. This knowledge can also help you write the correct observations and make inferences or conclusions about the
identities of anions and cations.
3. When carrying out tests on a salt:
(a) plan your experiment carefully
(b) be systematic and meticulous
(c) use correct techniques
(d) always follow safety procedures
4. The salt is dissolved in water or dilute acid.
5. The first step in qualitative analysis of a salt is to obtain an aqueous solution of the given salt.
6. A soluble salt will dissolve in water to produce ions in aqueous solution.
7. Insoluble salts such as an insoluble carbonate can be dissolved in dilute nitric acid to produce ions in aqueous
solutions.
Precipitation of Group I Cations

1. Prepare a mixture of Group I cations by adding 1.0 mL of each of the following aqueous solutions to a small
test tube: 0.1 M AgNO3AgNO3, 0.2 M Pb(NO3)2Pb(NO3)2 and 0.1 M Hg2(NO3)2Hg2(NO3)2. Note
that 1.0 mL is generally between 10-15 drops.
2. Pour 1.0 mL of the above mixture into a second small test tube and then add 2 drops of 6 M HClHCl to
this test tube.
3. Centrifuge the mixture from Step 2 in order to completely separate the solid precipitate from the solution.
Make sure that you balance the centrifuge before you start. Balancing is done by placing a test tube
containing water opposite to the test tube containing the precipitate in the centrifuge. The two test tubes
should have approximately equal weights.
4. Add one more drop of HClHCl to ensure that the precipitation is complete. If more precipitate is observed
then centrifuge the mixture again.
5. Decant the supernatant solution into another small test tube and save the precipitate for further study. The
supernatant solution may be discarded in the lab waste container.
Separation of Pb2+Pb2+ from Hg2+2Hg22+ and Ag+Ag+
6. Wash the precipitate from Step 5 to remove contaminates that may be trapped within the solid. This can be
accomplished by adding 1.0 mL of deionized water, stirring, and then centrifuging. Once again decant the
supernatant solution into a small test tube. Save the precipitate and discard the supernatant solution.
7. Prepare a hot water bath by adding tap water to a 250 mL beaker. Add water until the beaker is about one
half full. Assemble a stand, ring clamp and wire gauze to heat the water over the Bunsen burner until it is
boiling. Add 2.0 mL of deionized water to the test tube containing the clean precipitate and place it in the
hot water bath. Periodically stir the mixture in the test tube for 3-4 minutes.
8. Remove the test tube from the hot water bath and immediately centrifuge the hot mixture. Carefully decant
the hot supernatant solution into another small test tube. Save both the precipitate and the supernatant
solutions for further study.
9. In order to confirm the presence of Pb2+Pb2+, add 1 drop of 6 M HC2H3O2HC2H3O2 to the
supernatant solution obtained in Step 8. Next add 3-4 drops of 1 M K2CrO4K2CrO4. The formation of a
bright yellow precipitate is confirmation of the presence of the Pb2+Pb2+ ion.
Separation and Identification of Hg2+2Hg22+
10. Add 10-12 drops of 6 M NH3NH3 to the precipitate from Step 8, and mix thoroughly with your stirring rod.
11. The appearance of a gray solid is confirmation of the presence of Hg2+2Hg22+. Centrifuge the mixture
and decant the supernatant solution into another small test tube. Save the supernatant solution since it now
contains silver in the form of the aqueous Ag(NH3)+2Ag(NH3)2+ ion.
Identification of Ag+Ag+
12. To the solution obtained in Step 11, slowly add 6 M HNO3HNO3 until the solution is acidic to litmus paper.
The acidity can be tested by dipping a stirring rod into the solution and then touching it (with a drop of
solution) to a piece of blue litmus paper resting on a clean, dry watch glass. If the solution is acidic it will
turn blue litmus paper red or it will have no effect on red litmus paper. Formation of a white precipitate
of AgClAgCl in the acidic solution is confirmation of the presence of Ag+Ag+.

Part B: Analysis and Identification of Group I Cations in an Unknown Sample

1. Obtain a test tube which contains a mixture of Group I cations. Record the ID Code of the sample on your
Report Form
2. Pour 1.0 mL of the above mixture into a second small test tube and then add 2 drops of 6 M HClHCl to
this test tube
3. Continue following the same procedure used to analyze the known mixture of ions (Part A, Steps 3 – 13).
Note that you may observe either a positive or a negative result when you test for the presence of each ion
depending upon whether or not the ion is present in your unknown sample
4. On your Report Form, construct a flow chart similar to the one shown in the Background section of this lab.
Indicate on the flow chart whether the test for each ion is positive or negative. Then, in the space provided,
indicate which ions are present in your unknown sample
Lab Report: Qualitative Analysis of Group I Cations
Name: ____________________________ Lab Partner: ________________________

Date: ________________________ Lab Section: __________________

In the space provided below construct a flow cart for the analysis of your unknown. Indicate on the flow chart
whether the test for each ion is positive or negative:

Unknown ID number: __________________

Ions present in your unknown: ____________________________________

Pre-Laboratory Assignment: Qualitative Analysis of

Group I Cations
1. In order to identify Ag+Ag+, the solution must be acidified before a precipitate can form. Why?

2. A solution may contain one or more of the Group I cations. A white precipitate forms when 6 M HClHCl is added
to the solution. The precipitate is insoluble in hot water. The precipitate is then found to be completely soluble in 6
M NH3NH3. Indicate whether each of the following cations is present, undetermined, or absent.

 Pb2+Pb2+_____________________
 Hg2+2Hg22+_____________________
 Ag+Ag+______________________

Explain.
Preparation of Known Solution and Separation
of Cr3+Cr3+ and Al3+Al3+ from Fe3+Fe3+ and Ni2+Ni2+

1. Prepare a mixture of Group III cations by adding 1.0 mL of each of the following
0.1 M aqueous solutions to a small test
tube: Cr(NO3)3Cr(NO3)3, Al(NO3)3Al(NO3)3, Fe(NO3)3Fe(NO3)3, and Ni(NO3)2Ni(NO3)2.
Transfer 2.0 mL of this mixture to a 30-mL beaker and use it for your positive
control experiment.
2. Add 2 mL of 6 M NaOHNaOH to the 30-mL beaker containing your positive control
solution. Boil the solution very gently (use a pair of beaker tongs to hold the
beaker) over an open Bunsen burner flame for about one minute. Note that the
time to boil is variable and depends on the volume of solution you have. Do not
boil the solution to dryness. If you boil the solution to dryness, then you must
repeat this step again.
3. Remove the beaker from the flame and slowly add 2 mL of 1 M NaClONaClO.
Swirl the beaker for 30 seconds using your beaker tongs, then gently boil the
mixture for about one minute.
4. Again, remove the beaker from the flame and add sixteen drops of 6M NH3NH3.
Swirl the mixture, then gently boil for another minute.
5. Transfer the mixture from the beaker into a small test tube and centrifuge in
order to separate the solid from the solution. Decant the supernatant solution
(containing the chromium and the aluminum) into another test tube and save the
solid (containing the nickel and the iron). Save this supernatant solution for
further analysis. It contains the aluminum and chromium cations.
6. Wash the solid by adding 4 mL of water and twenty drops of 6 M NaOHNaOH. Stir
vigorously then centrifuge the mixture. Decant the supernatant solution into your
“waste” beaker and discard this solution.
7. Add 2 mL of 6 M HNO3HNO3 to the washed solid. Save the contents of this
test tube for further analysis. It contains the iron and nickel cations.

Separation of Al3+Al3+ from Cr3+Cr3+

8. Slowly add 6 M acetic acid to the supernatant solution saved from Step 5 until it
is acidic (test with blue litmus paper).
9. Add 6 M NH3NH3 one drop at a time until the solution just becomes basic again
(test with red litmus paper). Now add twenty additional drops of excess NH3NH3.
At this point a translucent, gelatinous precipitate of Al(OH)3Al(OH)3 should appear
in the clear (or pale yellow) solution.
10.Stir the mixture for about a minute to allow the system to reach equilibrium.
Centrifuge the mixture, then decant the supernatant solution into another small
test tube. This solution must be saved for further tests.
11.To wash the collected solid, first add 6 mL of deionized water to it. Then place
the test tube with the solid (and water) in a hot water bath for about two
 minutes while occasionally stirring the mixture. Check with your instructor if you
are unsure about how to set up a hot water bath. Finally, centrifuge this mixture
and decant the supernatant solution into your “waste” beaker. Discard the
solution and save the solid.

Confirmation of Al3+Al3+

12.To the solid from Step 11 add four drops of 6 M acetic acid and 6 mL of water.
Stir in order to dissolve the solid. Finally, add four drops of catechol violet to the
resulting solution. The appearance of a blue solution confirms the presence
of Al3+Al3+ in the original solution.

Confirmation of Cr3+Cr3+

13.To the decanted solution from Step 10, add twelve drops of 1 M BaCl2BaCl2. The
formation of a very fine, pale yellow precipitate (BaCrO4BaCrO4) confirms the
presence of Cr3+Cr3+ in the original solution.

Separation of Fe3+Fe3+ from Ni2+Ni2+

14.If the precipitate from Step 7 is not completely dissolved, stir it until it is
completely dissolved. If necessary, place the test tube in a hot water bath in
order to completely dissolve the precipitate.
15.Slowly add 6 M NH3NH3 to the solution until it is basic (test with red litmus
paper). You should see a red-brown precipitate of Fe(OH)3Fe(OH)3 appear when
the solution turns basic.
16.Add an additional 20 drops of 6 M NH3NH3 and stir to mix well. At this point the
nickel should be dissolved in the solution as Ni(NH3)6Ni(NH3)6.
17.Centrifuge the mixture and decant the supernatant solution into another test
tube. Save both the solid and solution.

Confirmation of Ni2+Ni2+

18.Add eight drops of dimethylglyoxime to the solution saved in Step 17. The
appearance of a rose-red precipitate confirms the presence of Ni2+Ni2+ in the
original solution.

Confirmation of Fe3+Fe3+

19.To the precipitate saved in Step 17 add twelve drops of 6 M HClHCl. Next, add 4
mL of deionized water and stir well until the precipitate is completely dissolved.
Finally, add four drops of 0.5 M KSCNKSCN. The formation of a dark red solution
confirms the presence of Fe3+Fe3+ in the original solution.