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QUALITATIVE ANALYSIS OF GROUP III CATIONS

Introduction
The group III cations are sulfides insoluble in basic solution, also called as the Iron
group. The cations precipitated as sulfides at this stage are CO 2+ , Zn2+ , Mn2+ , Ni2+ , and Fe2+. If
any Cr 3+ and Al3+ ions are present, they will also precipitate, but as insoluble hydroxides.
In this experiment the objectives were:
1.) To separate the ions from each other ; and
2.) To identify the presence of these ions on the unknown.
Background Information
Cations are typically divided into Groups, where each group shares a common reagent that can be
used for selective precipitation. The Group III cations include Co 2+, Zn2+, Mn2+, Cr3+, Al3+, Fe2+, Fe3+and
Ni2+. The precipitating agent for Group III cations is H2S in basic medium thus it forms insoluble sulfides
or hydroxides in a basic solution saturated with H2S.
[Co(NH3)6]2+(aq) + 3H2S(aq) CoS(s) + 6NH4+(aq) + 2S2-(aq)
[Ni(NH3)4]2+(aq) + 2H2S(aq) NiS(s) + 4NH4+(aq) + S2-(aq)
Fe2+(aq) + 2OH-(aq) + H2S(aq) FeS(s)+ 2H2O(l)
2Fe3++ H2S + 2H2O(l) S(s) + 2Fe2+(aq) + 2H3O+(aq)
[Zn(NH3)4]2+(aq) + H2S(aq) ZnS(s) + 4NH4+(aq) + 2OH-(aq)
However, two of these cations do not produce sulfide as in the reaction
Al(OH)3(s) + 3H2S Al2S3 + 6H2O 2Al(OH)3(s) + 3H2O(aq)
Cr(OH)3(s) + 3H2S(aq) Cr2S3(aq) + 6H2O(l) 2Cr(OH)3(s) + 3H2S(aq)
Methodology

1. Placed 1 mL each of 0.01 M solutions of Co2+ , Ni2+, Fe2+, Mn2+, Al2+, Cr2+, and Zn2+; and a
solution containing all the cations into separate 25-mL test tubes. The solution was warm and 5
mL of 6N NH4Cl was added. Then, it was being alkaline by adding 6N NH4OH and 2 mL excess
was added. It was heated and saturated with H2S and was boiled for 1 minute and stand for 5
minutes. After which, it was filtered and washed twice with distilled water. The washing was
discarded.
2. The residue collected was transferred to a beaker and 25 mL of 1M HCl was added. It was stirred
in an ice bath for 5 minutes. After which, it was filtered and the filtrate was collected and the
residue was washed once with distilled water and the washing was added to the filtrate.
3. The residue was transferred into an evaporating dish and 5 mL of aqua regia was added. It was
evaporated into almost dryness, cooled, and added with 5 mL of distilled water and 1mL of 1M

4.

5.

6.

7.
8.

HCl. The dish was rotated to dissolve the solids and it was being alkaline by adding NH 4OH. The
following test were performed:
a. 5 drops of the solution was put into spot plate and it was acidify with acetic acid. Then, 2
drops of -nitroso--naphol was added.
b. 5 drops of the solution was put into spot plate and it was added with 2 drops of
dimethylglyoxime.
The filtrate obtained in step 2 was boiled off to remove H2S and the vapors were tested with lead
acetate paper. It was being alkaline with 0.1M NaOH and 2 mL excess was added. After it was
cooled down, 1 g of Na2O2 was added in small portions. It was boiled gently for 2 minutes,
cooled, and 10 mL of distilled water was added and then filtered.
The residue was washed twice with hot distilled water and the washing was discarded. The
following test were performed:
a. Permanganate test. 1 mL of the solution was put into a test tube, 1 mL of conc. HNO 3 and
a few crystals of NaBiO3 were added, and mixed.
b. Prussian Blue Test. 1 mL of the solution was put into a test tube and 1 mL of HCl and few
drops of K4Fe(CN)6 were added.
c. Thiocyanate Test. 1 mL of the solution was put into a test tube and 1 mL of NH 4CNS was
added.
The filtrate obtained in step 4 was acidified with 0.1M HNO 3 and 3 g of solid NH4Cl was added.It
was being alkaline with NH4OH and large excess was avoided. It was boiled for 1 minute. After
which, it was filtered and the filtrate was collected. The residue was dissolved in 0.1M HNO 3, and
0.5 mL of 3M NH4C2H3O2 and 0.5 mL aluminum reagent were added. It was mixed well and
being alkaline with NH4OH.
The filtrate obtained in step 6 was acidified with HC2H3O and 5 mL of 3M NaC2H3O2 was added.
It was heated to boiling and 1 mL of 0.1M BaCl was added. It was filtered and the filtrate was
being slightly alkaline with NH4OH and passed in H2S.
The unknown mixture reserved in the previous experiment was obtained. Before analyzing which
ions were present in the unknown, it was being sure that the solution did not contain phosphate,
since the schematic diagram for the analysis of an unknown was derived from the results of the
analysis of known sample that contains phosphate. Phosphate interfered with the reactions on the
separation of the ions, so before analyzing the unknown, the following test for phosphate were
performed:
a. 1 mL of unknown sample was put in a test tube and 3 mL 6N HNO3 and 4 mL ammonium
molybdate were added. The solution was warm in boiling water bath. A yellow
precipitate was the indication of the presence of phosphate.
b. If the phosphate was absent, the analysis continued using the schematic diagram. After
precipitating the Group III cations with H2S, the filtrate was acidified with acetic acid,
boiled until H2S was removed ad tested with lead acetate paper. It was evaporated to
about 30 mL and put in a labeled bottle and reserved for the analysis of Group IV-V
cations in the next experiment.
c. If phosphate was present, took the unknown sample and 2-3 drops of conc. HNO 3 was
added. It was boiled for 2 minutes to insure the oxidation of iron to ferric state. It was the
point that the iron was tested, since ferric chloride will be used in the phosphate
separation. In doing it, few drops of K4Fe(CN)6 was added to 0.5 mL of the unknown
sample. A dark blue precipitate indicated the presence of iron.
d. To the HNO3 solution of the unknown sample, after this completed oxidation, NH4OH
was added drop by drop until the mixture was slightly alkaline. HCl was added drop by
drop until most of the precipitate was dissolved, leaving only a slight turbidity. 10 mL of
3M ammonium acetate and 10 mL of 3M acetic acid were added which precipitated the
phosphate as FePO4. If the solution mixture was not red or reddish brown, FeCl 3 solution
was added drop by drop until the entire mixture became rusty red. It was diluted to about

60 mL with distilled water. It was boiled slowly until the precipitates had coagulated
leaving a clear solution. It was filtered at once while hot and the filtrate was collected.
The precipitate was washed with hot distilled water and the washing was combined to the
filtrate. The filtrate possibly contained Co2+, Ni2+, Mn2+, Zn2+; and the ions of group IV
and V along with some colloidally suspended basic acetates. The filtrate was evaporated
to about 15 mL, any precipitate formed was discarded, and it was analyzed according to
the schematic diagram. After precipitating the Group III cations with H 2S, the filtrate was
acidified with acetic acid, boiled until H2S was removed using the lead acetate paper. It
was then evaporated for about 30 mL, out in a labeled and reserved for the analysis of
Group IV-V cations in the next experiments.
e. The residue contained mostly of ferric phosphate, FePO4, and basic ferric acetate,
Fe(OH)2C2H3O2, possibly mixed with smaller amounts of the phosphate and basic
acetates of Al3+ and Cr3+. Transfer the precipitate to an evaporating dish, 5 mL of distilled
water and 0.5 g Na2O2 were added. It was boiled for 1 minute, cooled, diluted with 10 mL
of distilled water, and filtered. The precipitate was discarded. The filtrate was being
slightly acidified with HNO3 and HN4OH was added until alkaline. A white precipitate
might be Al(OH)3 or AlPO4. It was filtred and the presence of aluminum was confirmed
by aluminum test on the precipitate. The filtrate was being acidified with acetic acid, and
BaCl2 was added. A yellow precipitate confirmed chromium.
Results and Discussion
Table 1 presents the observations for the Group 3 cations (Co 2+, Ni2+, Mn2+/Mn4+, Fe2+/Fe3+, Al3+,
Cr , Zn2+). When these cations were added with 5mL 6N NH 4Cl: Co2+ which is pink turned to light pink,
Ni2+ which is dark green turned to green, Fe 2+/Fe3+ which is yellow turned to light yellow, Mn2+/Mn4+, Al3+,
and Zn2+ which are colorless remained colorless, Cr 3+ which is pale blue became colorless, and the
solution mixture of all the ions turned to light brown with brown precipitates formed. When the solutions
were made alkaline with 6N NH 4OH and were added 2mL excess: Co 2+ solution became peach in color,
Ni2+ solution turned blue green, Mn2+/Mn4+ solution formed a light brown precipitate and supernate,
Fe2+/Fe3+ solution formed a reddish brown precipitate, Al 3+ solution formed a white precipitate, Cr3+
solution formed pale blue precipitate, Zn2+ solution remained colorless, and the solution mixture formed a
brown precipitate and a blue supernate. After passing H 2S: Co2+, Ni2+, and Fe2+/Fe3+ solutions formed
black precipitates, Mn2+/Mn4+ solution formed a peach precipitate, Al 3+ and Zn2+ solutions formed white
precipitates, Cr3+ solution formed a blue precipitate, and the solution mixture formed brown and black
precipitates. When 25mL 1M HCl (cold) were added to each of the mixture: Ni 2+ mixture formed black
crystals and the filtrate turned black, the precipitates of Mn 2+/Mn4+, Zn2+, Al3+, and solution mixtures were
not dissolved, some of the precipitates of Fe 2+/Fe3+ mixture were dissolved and some were not, and lastly,
the precipitates of Cr3+ mixture were dissolved.
3+

Table 1: Observations for group 3 cations after undergoing several processes


CATION
Adding NH4Cl
Adding NH4OH
Passing H2S
Adding HCl
(cold)
Co2+
The color
The color turned
Black
became light
to peach.
precipitates
pink.
were formed.
Ni2+
The color
Blue-green
Black
The black
became green.
solution was
precipitates
precipitates
formed.
were formed.
became black
crystals and the

Mn2+/Mn4+

Still colorless

Fe2+/Fe3+

The color
became light
yellow.

Al3+

Still colorless

Cr3+

It became
colorless.
Still colorless

Formed a light
brown
precipitate and
supernate.
Formed reddish
brown
precipitate.

Peach
precipitates
were formed.

White
precipitates
were formed.
Formed pale
blue precipitate.
Still colorless
Formed brown
precipitates and
a blue
supernate.

White
precipitates
were formed.
Formed blue
precipitates.
White
precipitates
were formed.
Brown and
black
precipitates
were formed.

Table 2: Reactions that took place during the process


CATION
Adding NH4Cl
Adding NH4OH

Passing H2S

Zn2+
Solution
Mixture

The color
became light
brown with
brown
precipitates.

Black
precipitates
were formed.

filtrate became
black.
The precipitates
were not
dissolved.
Some
precipitates
were dissolved
and some were
not.
The precipitates
were not
dissolve.
The precipitates
were dissolved.
Precipitates
were not
dissolved.
The precipitates
were not
dissolved.

Adding HCl
(cold)

Co2+
Ni2+
Mn2+/Mn4+
Fe2+/Fe3+
Al3+
Cr3+
Zn2+
Solution
Mixture
Conclusion
The following conclusions were formulated based on the results above which was performed
completely: (1) Addition of NH 4CNS to Fe3+ solution results to blood red in color, (2) Addition of
K4Fe(CN)6 to Fe3+ forms blue precipitates, (3) NH 4C2H3O2, Aluminon and NH4OH to Al3+ solution forms
red lake in indefinite composition in the bottom of the solution and (4) only Ni 2+ cation was determined in
the unknown solution.
References

Cabigon, L.G. 2013. Laboratory Manual for General Inorganic Chemistry II Vol. 2. Philippines: Central
Mindanao University
Qualitative Analysis of Cations (2003). Chemlab, Dartmounth College
Thompson, R. (2008) Illustrated Guide to Chemistry Experiment. OReilly Media Inc.
Zumdahl, S. (2015). Chemistry, An Atoms First Approach. (2nd Ed.) Cengage Learning