Name:____________________________________ Course:__________________ Score:

Date:_____________________________________ Group No:________________

Experiment No. 9
REACTION OF THE AMMONIUM SULFIDE GROUP
(IONS ARE SEPARATED AS SULFIDES IN THEIR ALKALINE SOLUTIONS)

I.OBJECTIVES:
1.
2.

III. DISCUSSION

Group reagent: Hydrogen sulfide in the presence of NH4+ ions.

Metals of this group form chlorides that are soluble in water, their sulfides are soluble in
dilute acids but are insoluble in ammoniacal solutions. They are separated as sulfides or hydroxides
by ammonium sulfide or hydrogen sulfide in a solution of ammonia and ammonium chloride. This
group is also called Alumminum-Iron Group and is divided into 2 subgroups:

1. Aluminum subgroup – whose hydroxides are soluble in excess NaOH and Na2O2.
2. Iron subgroup – whose hydroxides are insoluble in excess NaOH and Na2O2.

The members of the groups are:

Group III-A (Aluminum Subgroup) Group III-B (Iron Subgroup)

Al3+ - aluminum Fe2+ and Fe3+ - ferrous and ferric
Cr3+ - chromium Mn2+ - manganese (II)
Zn2+ - Zinc Co2+- cobalt (II)
Ni2+ - nickel (II)

ALUMINUM SUBGROUP (GROUP III – A)

Except for zinc ion, the sulfides of this group do not precipitate as such due to hydrolysis.
Zinc is classified under this grouping because, like aluminum and chromium, it forms an
amphoteric hydroxide which is very soluble in NaOH and Na 2O2 mixture. They form complex
ions as aluminate, chromate and zincate. This property is used to separate aluminum subgroup
from the iron subgroup.

ALUMINUM

The Ion. Aluminum exhibits only one oxidation state, +3 in its compounds. The common
salts of this ion are colorless and are appreciably soluble in water or dilute acid solution. Its
hydroxide is decidedly amphoteric, hence a series of complex compounds are formed in which
aluminum is a part of the complex as an aluminate, AlO2 ion.
Compounds of Aluminum
a. Aluminum hydroxide, Al(OH)3

1. NH4OH yields a white gelatinous precipitate of Al(OH)3 which is insoluble in the

excess of the reagent.

Al(NO3)3 + 3 NH4OH = Al(OH)3 + 3 NH4NO3

2. NaOH yields a white gelatinous precipitate of Al(OH)3 which readily dissolves in

the excess of the reagent forming aluminates.

Al(NO3)3 + 3 NaOH = Al(OH)3 + 3 NaNO3

Al(OH)3 + NaOH = NaAlO2 + H2O

b. “Lake formation”. Al(OH)3, being a positive colloid (carries a positive electric charge),
when mixed with a salt of a dye, and the mixture made alkali, an insoluble “lake” with
a distinctive color is formed. Thus, aluminon reagent an ammonium salt of
aurintricarboxylic acid, gives a bright red lake with Al(OH) 3.

c. Cobalt and aluminate, Co(AlO2)2, When Al(OH)3 is ignited, aluminum oxide, Al2O3, is
formed and this compound has acidic properties and combines with certain other oxides
at high temperature forming aluminates. If a mixture of Co(NO 3)2 and Co(NO3)2 is
fused, their respective oxides are first formed, then these will unite giving a blue residue
called cobalt alluminate.

Co(NO3)2 = CoO

+ Co(AlO2)2

Al(NO3)3 = Al2O3 “Thernard’s blue”

CHROMIUM

The Ion. Chromium shows three oxidation states in its various compounds: +2 in chromous
compounds, +3 in chromic, and +6 in chromates and dichromates. Chromous ion, Cr 2+ is easily
oxidized into the chromic condition. Chromic, Cr 3+ ion resembles Al3+ ion in several ways. It is
readily hydrolyzed with the formation of Cr(OH)3 which possess amphoteric properties. Oxidation
of the Cr3+ ion gives rise to the formation of chromates, CrO42- and dichromates, Cr2O72- depending
on the alkalinity or acidity of the medium.

Compounds of Chromium
 a. Chromic oxide, Cr2O3. The hydrolysis of the chromium salts gives rise to a hydrated
oxide, Cr2O3 . H2O. This so-called “hydroxide” which is precipitated from chromium
solution is described as hydrated oxide and is formed by the reaction of NH4OH or
(NH4)2S with solutions of chromic salts.

2 Cr(NO3)3 + 6 NH4OH = Cr2O3 H2O + 6 NH4NO3 + 2 H2O

2 Cr(NO3)3 + 3 (NH4)2S + 4 H2O = Cr2O3 H2O + 6 NH4NO3 + 2 H2S

In the presence of excess alkali hydroxide, the hydrated oxide dissolves forming another
series of compounds known as chromites.

2 Cr(NO3)3 + 6 NaOH = Cr2O3 . H2O + 6 NaNO3 + 2 H2O

Cr2O3. H2O + 2 NaOH (excess) = 2 NaCrO2 + 2 H2O

b. Oxidation to chromates by peroxides. Sodium peroxide or hydrogen peroxide solution in

alkaline medium, oxidizes Cr3+ into the yellow CrO42-, the chromium ion of which has an
oxidation state of +6 . When Na2O3 is added to the chromite solution, the latter is
oxidized forming a yellow solution of sodium chromate.

2 NaCrO2 + 2 Na2O2 + H2O = 2 Na2CrO4 + 4 NaOH

ZINC

The Ion. Zinc shows only one series of compounds in which the oxidation state is +2.
Zinc hydroxide possesses amphoteric properties forming zincates. Its most stable complex ions
are Zn(NH3)42+, Zn(CN)43-, HZnO2.

Compounds of Zinc

a. Zinc hydroxide, Zn(OH)2. Zinc hydroxide is separated as a white gelatinous

precipitate upon addition of the OH ions to the solutions of zinc salts.

b. Zinc complexes

1. Sodium zincate, Na2ZnO2. When an alkali hydroxide is added to a solution of

a zinc salt, a white gelatinous precipitate of Zn(OH) 2 is first formed which
dissolves upon addition of an excess reagent.

Zn(NO3)2 + NaOH = Zn(OH)2 + 2 NaNO3

 Zn(OH)2 + NaNO2 + 2 NaOH = Na2ZnO2 + NaNO3 + 2 H2O

2. Cobalt zincate, CoZnO2, when a mixture of Zn(NO3)2 and Co(NO3)2 is

evaporated to dryness and the residue ignited, the ZnO and coO formed will
unite forming a green CoZnO2, cobalt zincate, also known as Rinmann’s green.

An excess of the Zn(NO3)2 should be added because the an excess of oO that

may be formed, makes the green.

Zn(NO3)2 + Co(NO3)2 = ZnO + CoO = CoZnO2

c. Zinc potassium ferrocyanide, Zn3K2[Fe(CN)6]2. Zn2+ ions react with potassium

ferrocyanide forming a white precipitate of zinc-potassium ferrocyanide which is
insoluble in HCl but soluble in ammonium hydroxide or other strong bases.

2 Zn(NO3)2 + K4Fe(CN)6 = Zn2Fe(CN)6 + 4 KNO3

3 Zn2Fe(CN)6 + K4Fe(CN)6 = 2 Zn3K2[Fe(CN)6]2

d. Zinc sulfide, ZnS. Zinc sulfide is the only common white metallic sulfide. It is
precipitated by the addition of an alkali or ammonium sulfide to the solution of zinc
salts.
Zn(NO3)2 + H2S = ZnS +2 HNO3

GROUP III-B (IRON SUBGROUP)

The hydroxides of the members if this subgroup do not dissolve in excess sodium
hydroxide and Na2O2 – the mixture used to separate the 2 subgroups by Group III. This group
precipitates as sulfides in the process of separating these cations from the subsequent group. Their
ions do not display amphoteric properties.

IRON

The Ion. Iron forms two important series of salts: ferrous, with an oxidation state of +2
and ferric with an oxidation state of +3. The ferrous salts forms green hydrates while the hydrated
ferric salts are yellow or brown in color. The ferrous ion is a strong reducing agent having a
pronounced tendency to go to the ferric state.

Compounds of Iron
a. Ferrous and ferric hydroxide, Fe(OH)2 and Fe(OH)3. These hydroxide are precipitated by
NH4OH, NaOH, or KOH when these reagents are added to neutral solutions of ferrous or
ferric salts.

For ferrous salts: FeCl2 + NaOH = Fe(OH)2 + 2 NaCl

FeCl2 + NH4OH = Fe(OH)2 + 2NH4Cl

Ferrous hydroxide is white when pure but is rapidly oxidized in air, undergoing several
stages of color: first, green, then it turns black and finally reddish-brown when it becomes
Fe(OH)3.

2 Fe(OH)2 + H2O (oxidized in air) = 2 Fe(OH)3

For ferric salts: FeCl3 + 2 NaOH = Fe(OH)3 + 3 NaCl

FeCl3 + NH4OH = Fe(OH)3 + 3 NH4Cl

Ferric hydroxide is insoluble in excess of the reagent and in this way differs from the
hydroxides of aluminum, chromium and zinc. It also differs from the hydroxides of cobalt
and nickel since tha latter are soluble in excess NH4OH forming complex ions.

b. Sulfides of iron. FeS and Fe2S3. Ferrous sulfide is a black precipitate formed when soluble
sulfides are added to neutral or basic solutions of ferrous salts.

Fe(OH)2 + H2S = FeS + 2 H2O

Fe(OH)2 + Na2S = FeS + 2 NaOh
Fe(OH)2 + (NH4)2S = FeS + 2 NH4OH

Hydrogen sulfide in acid solution reduces ferric to ferrous with the precipitation of sulfur.

2 Fe(NO3)3 + H2S = 2 Fe(NO3)2 + 2 HNO3 + S

But if ammonium sulfide in alkaline solution is used, Fe 2S3 is precipitated.

2 Fe(NO3)3 + 3 (NH4)2S = Fe2S3 + 6 NH4NO3

2 Fe(OH)3 + 3 (NH4)2S = Fe2S3 + 6 NH4OH

c. Complex iron cyanides.

1. Ferrous and ferric ferrocyanide. Potassium ferrocyanide yields with solution of ferrous
salts, a white precipitate of ferrous ferrocyanide with complete exclusion of air. In the
 presence of air, the precipitate is greenish or light blue in which case Fe 2+ ion is
oxidized to Fe3+ state.

2 KeSO4 + K4Fe(CN)6` = Fe2Fe(CN)6 + 2 K2SO4

ferrous ferrocyanide

6 Fe2Fe(CN)6 + 6 H2O + 3 O2 (air) = 2 Fe4[Fe(CN)6]3 + 4 Fe(OH)3

ferric ferocyanide

with ferric salts, the same precipitate ferric ferrocyanie (or Prussian blue) as above, is
obtained:

4 Fe(NO3)3 + 3 K4Fe(CN)6 = Fe4[Fe(CN)6]3 + 12 KNO3

Prussian blue

2. Ferrous and ferric ferricyanide. Potassium ferricyanide yields with ferrous salts, a
blue precipitate (Turnbull’s blue) of ferrous ferricyanide.

3 KeSO4 + 2 K3Fe(CN)6 = Fe3[Fe(CN)6]2 + 3 K2SO4

Turnbull’s blue

Ferric salts gives a brown solution with the same reagent due to the formation of a
ferricyanide or simply, ferric cyanide.

Fe(NO3)3 + K3Fe(CN)6 = 2 Fe(CN)3 or FeFe(CN)6 + 3 KNO3

ferric cyanide (brown solution)

d. Ferric thiocyanate, Fe(SCN)3. Ammonium or potassium thiocyanate gives a blood-red

colorations with ferric ions.

Fe(NO3)3 + 3 KSCN = Fe(SCN)3 + 3 KNO3

blood-red color

MANGANESE

The Ion. Manganese forms several series of compounds with the oxidation states ranging
from +2 to +7. These ions with their corresponding names and compounds are the following:

Ion Name Compound

Mn2+ manganous Mn(OH)2

 Mn3+ manganic Mn(OH)3
Mn4+ manganese MnO2
Mn6+ manganite K2MnO4
Mn7+ permanganate KMnO4

Compounds of Manganese
a. Manganous hydroxide, Mn(OH)2. This is a white precipitate obtained when ammonium
hydroxide or alkali hydroxide us added to a neutral solution of Mn 2+ ions. But when in
contact with air, it becomes brown.

Mn(NO3)2 + 2 NH4OH = Mn(OH)2 + 2 NH4NO3

Mn(NO3)2 + 2 NaOH = Mn(OH)2 + 2 NaNO3

b. Manganous sulfide, MnS. Solutions containing Mn2+ ions when treated with
ammonium sulfide, will produce a salmon-colored precipitate of MnS which is readily
soluble in acids even in the weak acetic acid.

Mn(NO3)2 + (NH4)2S = MnS + 2 NH4NO3

Mn(NO)2 + (NH4)2S = MnS + 2 NH4OH

c. Oxidation of Mn2+ ion.

1. Manganous compounds are readily oxidized by Na2O2 to dark brown

precipitate.

Mn(OH)2 + Na2O2 = MnO2 + 2 NaOH

2. Manganous compounds are also oxidized by BaBiO3, sodium bismuthate,

with the the development of a purple or violet or pink coloration (depending
on the amount of Mn2+ ions present).

2 Mn(NO3)2 + 5 NaBiO3 + 16 HNO3 = 2 HMnO4 + 5 NaNO3 + 5 Bi(NO3)3 + 7 H2O

COBALT

The Ion. Cobaltous, Co2+ form is the only simple ion of cobalt that is of analytical
importance. Hydrated cobaltous compounds and their dilute solutions are pink in color, while
concentrated solutions and the anhydrous salts are blue.
Compounds of Cobalt

a. Cobalt hydroxide, Co(OH)2. Alkali hydroxides precipitate cobalt hydroxide from

solutions of cobalt salts. The hydroxides is blue in color in cold solutions but pink or
rose-red in warm solutions.

Co(NO3)2 + 2 NaOH = Co(OH)2 + 2 NaNO3

The precipitate formed is only very slightly soluble in excess alkali. On exposure
to air, Co(OH)2 becomes brown in color due to partial oxidation.

b. Oxidation of cobalt. When Cobalt hydroxide is treate with Na 2O2, a brown to black
precipitate of cobaltic hydroxide, Co(OH)3 is formed.

2 Co(OH)2 + Na2O2 + 2 H2O = Co(OH)3 + 2 NaOH

c. Cobalt sulfide, CoS. Cobalt sulfide is a black precipitate obtained in an ammoniacal

solution of Co2+ ions with (NH4)2S.

Co(NO3)2 + (NH4)2S = CoS + 2 NH4NO3

d. Cobalt ammonia complex ion, Co(NH3)42+. Ammonium hydroxide when added to

solutions of cobalt ions precipitate Co(OH)2, but this is soluble in excess of the reagent
and in excess of NH4Cl. The dirty yellow ammoniacal solution gradually turns to
reddish in color on exposure to air due to the formation of the more stable
cobalt=ammonia complex ion.

e. Cobaltinitrite ion, Co(NO2)63. Potassium nitrate added to solution of Co2+ which have
been acidified with acetic acid, gives a yellow precipitate of potassium cobaltinitrite.

Co(NO3)2 + 7 KNO2 + 2 CH3COOH = K3Co(NO2)6 + 2 CH3COOK + NO + 7 KNO3 + H2O

NICKEL

The Ion. The principal oxidation state of nickel is +2. Nickel salts in the hydrated form
and in solution, are green in color, while the anhydrous salts are yellow.

Compounds of Nickel

a. Nickel hydroxide, Ni(OH)2. It is a green precipitate obtained by the reaction between

Ni2+ ions and alkali hydroxides.

Ni(NO3)2 + 2 NaOH = Ni(OH)2 + 2 NaNO3

 b. Nickel ammonia complex, Ni(NH3)62+. Ammonium hydroxide in dilute solution and
in the absence of ammonium salts, precipitate a green basic salt soluble in excess of
the reagent forming a series of ammonia complex ions called nickel-ammines.

c. Nickel sulfide, NiS. Nickel sulfide is not precipitated by H 2S in solutions of nickel

salts containing mineral acids or much acetic acid, but from solutions made slightly
acidic with acetic acid and containing an alkali acetate, or from its ammoniacal
solution in which all nickel ions may be precipitated as black nickel sulfide.

Ni(NO3)2 + 2 CH3COONa + H2S = NiS + NaNO3 + CH3COOH

Ni(NH3)4(NO3)2 + H2S = NiS + 2 NH4NO3 + 2 NH3

d. Glyoxime derivative of nickel. Dimethyglyoxime in alcohol yields with solutions of

nickel salts made alkaline with ammonium hydroxide, a characteristic red precipitate
of nickel dimethylgloxime.

Ni(NO3)2 + 2 NH3 + 2 C4H6N2O2H3 = Ni(C4H6N2O2H2)2 + 2 NH4NO3

dimethylglyoxime nickel dimethylglyomoxime

III. MATERIALS

water bath filter paper burner tripod test tubes droppers

IV. PROCEDURE

4-1. In 8 separate test tubes, place 5 drops each of the following test solutions: Al3+, Cr3+, Zn2+,
Mn2+, Co2+, Ni2+, Fe2+, and Fe3+. Note the color of each test solution.

Al3+ _________ Zn2+ _________ Co2+ _________ Fe2+ __________

Cr3+ _________ Mn2+_________ Ni2+ _________ Fe3+ __________

4-2. Add 2 drops of an equal volume of 6N NH4OH and 6N NH4Cl (1 drop each) to each test
tube. Write the color of each precipitate under the column 4-2 in Table 4.

a. Add 1 drop of (NH4)S to the test tubes above (4-2) and note the color of the precipitate. Write
the color in row 4-2a in Table 4.

4-3. In 8 separate test tubes, place 5 drops each of the test solutions of Group III cations and add
1 drop of 6N NaOH to each test tube until a precipitate is formed. Write the color of each
precipitate in row 4-3 in Table 4.
a. Test the solubility of the precipitate above (4-3) by adding 2-3 drops more in excess of 6N
NaOH. Write your observations in row 4-3a in Table 4.
b. Then add 2 drops of H2O2 or a small amount of Na2O2. Stir and note what test tubes you have
observed a change. Write your observations in row 4-3b in Table 4.

4-4. Confirmatory Test for Al3+

a. Aluminon Test. To 2 drops of Al3+ test solution, add 6N NH4OH until a precipitate is formed.
Add 1 drop of 6N ammonium acetate and 2 drops of Aluminon reagent. Observe the color of the
lake. _________________

b. Thenard’s Blue Test. To 5 drops of Al3+ test solution, add 1 drop of Co(NO3)2 and 3-4 drops of
6N NH4OH. Filter and ignite the precipitate. Note the color of the ash. _______________

4-5. Confirmatory Test for Cr3+. To 5 drops of Cr3+ test solution, add 6N NaOH until a precipitate
which first formed dissolves. Then add H2O2 or Na2O2 until a change is observed. Add 6-8 drops
of distilled water. Stir and heat on a water bath for 5 minutes. Divide into 4 portions in 4 separate
test tubes.

a. To the first portion, add AgNO3. Color of precipitate: ________________________

b. To the second portion, add BaCl2. Color of precipitate: _______________________

c. Acidify the third portion with acetic acid and add 1 drop of lead acetate. Observe the color of
the precipitate. ______________________

d. Reserve the fourth test tube for comparison. Observe the color of solution. _______________

4-6. Confirmatory Test for Zn2+

a. To 5 drops of Zn2+ test solution, add 3-5 drops of K4Fe(CN)6.

Color of precipitate: ___________________

b. Rinmann’s Green. To 6 drops of Zn2+ test solution, add 1-2 drops of cobalt nitrate and a few
drops (about 4-7 drops) of 6N NH4OH. Filter and ignite the precipitate. Note the color of the ash.
____________________

4-7. Confirmatory Test for Mn2+. To 2 drops of Mn2+ test solution, add 2 drops of 3N HNO3.
Introduce a bit of sodium bismuthate. Note the color of the solution. _________________

4-8. Confirmatory Test for Fe3+. In 3 test tubes, add 3 drops of Fe3+ solution, and add the following
reagents:

a. 3 drops of KCNS to the first test tube. Observe the change. ________________________

b. 3 drops of K4Fe(CN)6 to the second test tube. Observe. __________________________

c. 3 drops of K3Fe(CN)6 to the third test tube. Observe. ____________________________
4-9. Confirmatory Test for Fe2+. In 3 separate test tubes, add 3 drops of Fe2+ and add the
following reagents:

a. 3 drops of KCNS to the first test tube. Observe the change. ________________________

b. 3 drops of K4Fe(CN)6 to the second test tube. Observe. __________________________

c. 3 drops of K3Fe(CN)6 to the third test tube. Observe. ____________________________

4-10. Confirmatory Test for Co2+. To 5 drops of Co2+ test solution, add 3 drops of 6N KNO2 and
1-2 drops of acetic acid. Stir the mixture and heat almost to boiling in a water bath. Note the
crystals produced. __________________________________

4-11. Confirmatory test for Ni2+. To 5 drops on Ni2+ test solution, add 1 drop of concentrated
NH4OH and 3 drops alcoholic dimethyl glyoxime. Note the color of the precipitate.
______________________

V. CONCLUSION
COMPLETE THE TABLE.
TABLE 4-A

COLOR, NAME AND FORMULA OF THE

CONFIRMATORY TEST
PRECIPITATE OR SOLUTION

4-4a. Al3+, NH4OH, NH4Ac, Aluminon

Reagent

4-4b. Al3+, Co(NO3)2, NH4OH

4-5. Cr3+, NaOH, H2O2 or Na2O2

a. Above solution, add AgNO3

4-5b. Solution in 4-5, add BaCl2

4-5c. Solution in 4-5, add PbAc2

4-5d. Solution in 4-5

4-6a. Zn2+, K4Fe(Cn)6

4-6b. Zn2+, Co(NO3)2, NH4OH. Precipitate

ingnited.

4-7. Mn2+, HNO3, sodium bismuthate

4-8a. Fe3+, KCNS

4-8b. Fe3+, K4Fe(Cn)6

4-8c. Fe3+, K3Fe(CN)6

4-9a. Fe2+, KCNS

4-9b. Fe2+, K4Fe(Cn)6

4-9c. Fe2+, K3Fe(CN)6

4-10. Co2+, KNO2, CH3COOH

4-11. Ni2+, NH4OH, alcoholic dimethyl

glyoxime