Qualitative analytical chemistry I experiments

Qualitative Analysis
of
The Group I Cations

Wimbo triono
3315081900

University of Jakarta
I. Purpose

1. Separating the group I cations from sample

2. Indentifying the group I cations use specific reagent

3. Knowing chemical properties of group I cations

II. Basic of theory

In the classical qualitative analysis scheme, the first ion which

are determined are Ag+, Pb2+, and Hg22+. Of all the commons
cations, only these form insoluble chlorides under acidic conditions.
These cations comprise Group I in the scheme and are separated
from general salt solution by precipitation of their chlorides at a pH
of about zero. The chloride precipitate is then analyzed the possible
presence of silver, lead and mercury (I) on the basic of the
characteristic properties of those cations.

Silver has only a few water soluble salts, of which the nitrate is
certainly the most common. Most of the insoluble silver salts
dissolve in cold 6 M HNO3, the main exceptions being the silver
halides, AgSCN and Ag2S. Silver ion forms many stable complexes;
of these, the best known is probably the Ag(NH3)2+ ion. This comlex
is sufficiently stable to be produce when AgCl or AgSCN is treated
with 6 NH3; the reaction which occurs is usefull for dissolving those
solids. AgBr and AgI are less soluble than AgCl; AgBr will go into
solution in 15 M NH3, but AgI is so insoluble that it will not. The silver
Thiosulfate complexe ion, Ag(S2O3)23-, is extremly stable, and is
important in photography, where it is formed in the “fixing” reaction
in which AgBr is removed from the developed negative.

Lead nitrate and acetate are the only well known soluble lead
salts. Lead chloride is not nearly as insoluble in water as are the
chlorides of silver and mercury (I), and becomes moderately soluble
if the water is heated. PbSO4 is ion of the relatively few insoluble
sulfates. Lead forms a stable hydroxide complex ion and a weak
chloride complex. Although lead ordinarily has an oxidation number
of +2, there are some Pb (IV) compounds, of which thenist cinnib us
PbO2 (brown), this compound is insoluble in most reagents, but will
dissolve in 6 M HNO3 to which some H2O2 has been added.
 Mercury (I) has only one soluble salt, the nitrate, and even with
this compound, excess HNO3 must be present to keep basic Hg(I)
salts from precipitating. The Hg(I) ion, sometimes called mercurous
ion, is relatively unstable, it will slowly oxidize to Hg(II) if exposed to
air, and can be reduced to the metal by reducing cations (e.g. Sn2+).
In the presence of species that reaction to Hg (solid, black) and the
Hg(II) compound. Mercury(I) chloride has a very characteristic
raction with amonia:

Hg2Cl2(s) + 2 NH3(aq) -> Hg(s) + HgNH2Cl(s) + NH4+(aq) + Cl-(aq)

III. Instruments and materials

• Instruments * Material

1. Pipete 1. HCl

2. Beaker glass 2. NH4OH

3. Semimicro test tube 3. Aquaregia

4. Centrifuge tube

5. Filter paper

6. funnel

IV. Procedure

1. To 3 ml of sample in a test tube, add 0,5 ml 6 M HCl. Stir well and

centrifuge. Decant the liquid, into a test tube. To make sure
precipitation of group I cations was complete, add 1 drop of 6 M
HCl to the liquid. Wash the precipitate with 2 ml water and 3
drops of 6 M HCl. Stir well sentrifuge and discard the wash liquid.
Wash the precipitate again with water and HCl, centrifuge and
discard the wash.

2. To the precipitate from step 1, which contains the chlorides of

the group I cations, add about 4 ml water. Heat in the boliling
water bath for at least three minutes, stirring constantly,
centrifuge quickly and decant the liquid, which may contains
Pb2+, in test tube

3. Confimation of the presence of lead. To the liquid from step 2

add 2 drops of 6 M acetic acid and 3 or 4 drops of 1 M K2CrO4.
 The formation of a yellow precipitate confirms the presence of
lead. Centrifuging out the solid may help with the identification,
because the liqiod phase is orange.

4. Confirmation of the presence of mercury. If lead is present, wash

the precipitate from step 2 with 6 ml water in the boiling water
bath. Centrifuge and test the liquid for Pb2+. Continue the
washings until no positive reaction to the lead test is obtained. To
the washed precipitate add 2 ml 6 M NH3 and stir well. A black or
dark gray precipitate estabilish the presence of the mercury (I)
ion. Centrifuge and decant the liquid, which may contain
Ag(NH3)2+, into test tube. Identifiying filtrat for Ag ion.

V. Data of experiments

sample Experiments result

Sample+HCL A white precipitate

Precipitate + Hot water Half of precipitate solute

Filtrate + K2CrO4 An yellow precipitate

…………+ NaOH Precipitate soluble

Precipitate + NH4OH A gray precipitate

Filtrate + KI A green precipitate

…………+ NaOH Precipitate soluble

…………+ K2CrO4 An orange precipitate

Precipitate + Aquaregia A white precipitate

Filtrate + KI A red precipitate

………..+ NaOH A white precipitate

VI. Analysis of data

 Sample that will identifying compose liquid and unknown
precipitate. So, precipitate in sample have to dissolved berfore
identification. Assume that dissolving used H2O will cause
precipitation of phosphate of group III, IV cations and magnesium,
dissolving sample used HNO3. The unknown precipitate had
dissolved.

HCl 6 M add into sample. A white percipitate formed and

establish the presence of group I cations. Chlorides from other
cations will dissolve, except group I cations. Centrifuge and decant
the liquid into test tube.

Ag+ + Pb2+ + Hg22+ -> AgCl(S) + PbCl2(s) + Hg2Cl2(s)

Precipitate which may contains Pb2+, Ag+ and Hg(I) wash with hot
water. PbCl2 which soluble in hot water will dissolve. The wash liquid
use for identification of Pb2+. The wash liquid divide into two test
tube. K2CrO4 added into first test tube, a yellow precipitate indicates
the presence of Pb2+. The second test tube added NaOH excess, no
precipitate result from these because Pb2+ will be complex ions with
hidroxide.

PbCl2(s) -> PbCl2(Aq)

PbCl2(aq) + K2CrO4 -> PbCrO4(s) + 2KCl

The precipitate from separating Pb2+ added NH4OH in order to

separate AgCl from Hg2Cl2. AgCl dissolve in NH4OH excess form ion
complex while Hg(I) form precipitate of Hg and Hg(NH2)Cl. A white
precipitate which slowly become gray indicates the presence of
Hg(I).

AgCl + NH3 -> [Ag(NH3)2]+ + Cl-

Hg2Cl2 + NH3 -> Hg(s) + Hg(NH2)Cl(s) + NH4+ + Cl-

Centrifuge and decant the liquid into a test tube. To confim the
presence of mercury, precipitate dissolved in aquaregia. The gray
precipitate become white because of Hg dissolve in HNO3 but
Hg(NH2)Cl not. A white precipitate indicates Hg(NH2)Cl. The liquid
added KI to make a red precipitate, from experiments red
precipitate formed and establish the presence of mercury in the
sample.
 Liquid from separating AgCl from Hg2Cl2 used to identify Ag+ in
sample. Based on experiments, the presence of Ag+ in sample
cannot be sure because the experiments results are different with
theory.

VII. Task

Write chemical equations for each step

• HCL 6 m

Ag+ + Pb2+ + Hg22+ -> AgCl(S) + PbCl2(s) + Hg2Cl2(s)

• Hot water

PbCl2(s) -> PbCl2(Aq)

• K2CrO4

PbCl2(aq) + K2CrO4 -> PbCrO4(s) + 2KCl

• NaOH

PbCl2 + 2NaOH -> Pb(OH)2(s) + NaCl

.............+ 2NaOH excess -> Na2[Pb(OH)4]

• NH3

AgCl + NH3 -> [Ag(NH3)2]+ + Cl-

Hg2Cl2 + NH3 -> Hg(s) + Hg(NH2)Cl(s) + NH4+ + Cl-

• HNO3

6Hg(s) + 8HNO3 -> Hg22+ + 2NO + 6NO3- + 4H2O

VIII. Conclusion

1. The Group I cations is presence in the sample

2. PbCl2 dissolve in hot water, but AgCl and Hg2Cl2 cannot

3. Identify Pb2+ use K2CrO4 and NaOH establish the presence of

Pb2+ in the sample
 4. Identify Hg22+ use NH3 establish the presence of Hg22+ in
sample

5. Sample contains lead and mercury

IX. Bibliography

Darsati, Siti, dkk. 1999. Dasar-Dasar Kimia Analitik. Bandung:

FMIPA UNJ

Haryadi, W. 1990. Ilmu Kimia Analitik Dasar. Jakarta: Gramedia

Khopkar, SM. 1990. Konsep Dasar Kimia Analitik. Jakarta: UI Press

Oktaviani, Isnania, P. 2008. Laporan Praktikum KA I. Jakarta: UNJ

Vogel. 1979. Analisis Anorganik Kualitatif Makro dan Semimikro.

Jakarta.: PT Kalman Media Pustaka