CONFIRMATORY TESTS

Confirmatory tests should be performed on separate solutions of some of your ions, in order to see
what these tests look like before using them on an unknown. Generally a confirmatory test is used
only after other reactions have been used to isolate the ion. When working with stock solutions of an
ion, dilute 1 drop with 9 drops of water to simulate the concentration that would exist in an unknown.
In a mixture or a solution obtained from an unknown or known mixture, the dilution is not necessary
since the ions have already been diluted compared to the stock solutions. In the tests described here,
it is assumed that 10 drops of solution will be used. If you change the amount of solution of the ion
being tested, you must also adjust the amounts of the reagents to be added.

Tests Based on Hydrogen Sulfide

Antimony, Sb3+

Cadmium, Cd2+

Mercury(II), Hg2+

Tests Based on Other Reagents

Aluminum, Al3+

Ammonium, NH4+

Bismuth, Bi3+

Calcium, Ca2+

Chromium, Cr3+

Cobalt, Co2+

Copper, Cu2+

Iron, Fe3+

Magnesium, Mg2+

Manganese, Mn2+

Mercury(I), Hg22+

Mercury(II), Hg2+

Nickel, Ni2+

Silver, Ag+

Strontium, Sr2+

Tin, Sn2+
Zinc, Zn2+

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A. Tests Based on Hydrogen Sulfide

Even if hydrogen sulfide was not used for separation of ions, it may be useful for confirmatory tests.

The most convenient and safe source of H2S is thioacetamide. When heated, aqueous solutions of
thioacetamide hydrolyze to produce H2S:

In acid solution:

CH3CSNH2 + 2H2O + H+ --> CH3COOH + NH4+ + H2S

In basic solution using ammonia:

CH3CSNH2 + 2H2O + 2NH3 --> CH3COO- + 3NH4+ + S2-

In basic solution using strong base:

CH3CSNH2 + 2OH- --> CH3COO- + NH3 + S2- + H2O

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Antimony, Sb3+

To 10 drops of solution, add 6 M NH3(aq) until neutral. Make the solution acidic by adding one or
more drops of 6 M HCl. Add 1 mL of thioacetamide and stir well. Heat the test tube in the boiling
water bath for 5 minutes. If antimony is present, a red orange precipitate of antimony sulfide should
form. This same test will also work with arsenic(III),

tin(II),

and tin(IV).
These precipitates are yellow, brown, and yellow, respectively.

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Cadmium, Cd2+

Three related procedures can be used.

a. Follow the procedure described for antimony(III). The precipitate should be yellow.

b. Follow the procedure described for antimony(III), but first make the solution basic with aqueous
ammonia. If a precipitate forms on addition of ammonia, continue to add ammonia until the precipitate
dissolves, before adding the thioacetamide.
c. Add ammonia, as described in procedure b. Then add 10 drops of water and 10 drops of 6 M
NaOH. A white precipitate should form. If it does not form, either increase the amount of NaOH, or do
not add the 10 drops of water. Centrifuge and discard the solution. Wash the precipitate twice with a
mixture of 1 mL of water and 1 mL of 6 M NH3(aq). Dissolve the precipitate by adding 6 M HCl drop by
drop until no precipitate remains. Add 6 M NaOH until the solution is just basic. A white precipitate of
Cd(OH)2 will form. Then add 1 mL of 1 M thioacetamide and heat the mixture in a boiling water bath
for 5 minutes. A yellow precipitate of CdS will form.

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Mercury(II), Hg2+

Follow the procedure described for antimony(III). The precipitate should be black.

Try to dissolve the precipitate in 1 mL of 12 M HCl with heating. If it does not dissolve in HCl, try the
same procedure with 1 mL of 6 M (dilute) HNO3. If it still does not dissolve, then try to dissolve it in a
mixture of 1 mL of 6 M HCl and 1 mL of 6 M HNO3, heating for 2 minutes in a water bath. Most of the
black precipitate should dissolve. Mercury(II) sulfide is the least soluble of the metal sulfides.
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Tests Based on Other Reagents

Aluminum, Al3+

To 10 drops of solution, add 2 drops of aluminon. Add 6 M NH3(aq) dropwise until the solution is basic
to litmus. White Al(OH)3 should form and adsorb the aluminon, which colors it red. The solution should
become colorless.

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Ammonium, NH4+

Place 10 drops of solution in a 30 mL beaker. Place a moistened piece of red litmus paper and put it
on the bottom of a small watch glass. Add 1 mL of 6 M NaOH to the sample in the beaker. Cover the
beaker with the watch glass. Gently heat the solution to near the boiling point. Do not allow the
solution to splatter onto the litmus paper. The paper should turn blue from ammonia fumes.
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Bismuth, Bi3+

Two procedures can be used.

a. To 10 drops of solution, add a freshly prepared sodium stannite solution dropwise. A black
precipitate should form.

Sodium Stannite: The sodium stannite solution is prepared by diluting 4 drops of 0.25 M SnCl 2 with 2
mL water and adding 6 M NaOH dropwise, stirring well after each drop, until a permanent precipitate
forms. Then add excess NaOH to dissolve this precipitate.

b. To 10 drops of solution, add 2 drops of 6 M HCl. Then add water dropwise until a white precipitate
forms. The precipitate may not be very pronounced, but may instead show up as a turbidity of the
solution.
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Calcium, Ca2+

Two procedures may be used.

a. To 10 drops of solution, add aqueous ammonia to make the solution basic. Then add
(NH4)2C2O4 (ammonium oxalate) solution dropwise. A white precipitate should form.

b. Perform a flame test. The flame should turn orange-red.

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Chromium, Cr3+

To 10 drops of solution, add 1 mL of 3% H2O2. Then add 6 M NaOH dropwise until the solution is
basic. Heat in a boiling water bath for a few minutes. A yellow solution of CrO 42- should form.
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Cobalt, Co2+

To 10 drops of solution, add 5 drops of 0.5 M KNCS. To this mixture, add an equal volume of acetone
and mix. A blue color indicates the formation of [Co(NCS)4]2-.

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Copper, Cu2+

To 10 drops of solution, add 0.5 M K4Fe(CN)6 dropwise until a red-brown precipitate forms.

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Iron, Fe3+

Two procedures can be used.

a. To 10 drops of solution, add 0.5 M K4Fe(CN)6 dropwise until a dark blue precipitate forms.

b. To 10 drops of solution, add 1 or 2 drops of 0.5 M KNCS. The solution should become deep red
due to formation of FeNCS2+.

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Magnesium, Mg2+

To 10 drops of solution, add 2 drops of magnesium reagent , 4-(p-nitrophenylazo)resorcinol. Then

add 6 M NaOH dropwise. A "blue lake" -- a precipitate of Mg(OH)2 with adsorbed magnesium reagent
-- forms.
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Manganese, Mn2+

To 10 drops of solution, add 1 mL of 6 M HNO3. Add a spatula-tip quantity of solid sodium bismuthate
(NaBiO3) and stir well. There should be a slight excess of solid bismuthate. Wait about 1 minute and
then centrifuge the mixture. The solution should be purple due to the presence of MnO 4-.

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Mercury(I), Hg22+

To 10 drops of solution, add 6 M HCl to form a white precipitate. Centrifuge and discard the
centrifugate. Add 6 M NH3(aq) to the precipitate. The color of the precipitate should change to gray or
black due to formation of mercury metal.

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Mercury(II), Hg2+
To 10 drops of solution, add 1 or more drops of 0.25 M SnCl2. A grayish precipitate should form. The
precipitate might be white or black instead of gray.

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Nickel, Ni2+

To 10 drops of solution, add 6 M NH3(aq) until the solution is basic. Add 2 or 3 drops of
dimethylglyoxime reagent (DMG). A rose-red precipitate of Ni(DMG)2 should form.

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Silver, Ag+

To 10 drops of solution, add 6 M HCl dropwise, with shaking, until precipitation is complete.
Centrifuge and decant. Discard the centrifugate. Suspend the silver chloride precipitate in 1 mL of
water and add 6 M NH3(aq) dropwise until the precipitate dissolves. Acidify the solution with 6 M
HNO3 and the white precipitate should reappear.
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Strontium, Sr2+

To 10 drops of the solution , add 5 drops of ethanol (C2H5OH). Then add 3 M (6 N) H2SO4 dropwise
until precipitation is complete. Heat the sample in a water bath for a few minutes. Test again for
complete precipitation by adding 1 more drop of sulfuric acid. Centrifuge and decant the supernatant.
If any further tests will be carried out on the supernatant liquid, heat it in a boiling water bath to expel
the C2H5OH, which could interfere with further tests. The white precipitate of SrSO 4 confirms the
presence of strontium.

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Tin, Sn2+

To 10 drops of solution, add 1 or 2 drops of 0.2 M HgCl2. A white precipitate should form, but it could
be gray or black instead.
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Zinc, Zn2+

To 10 drops of solution, add 6 M NH3(aq) to give a neutral pH. Then make the solution slightly acidic
to litmus paper with 6 M HCl. Add 1 or 2 drops of 0.5 M K4Fe(CN)6 and stir. A gray-white precipitate of
K2Zn[Fe(CN)6]2 is formed.

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