QUALITATIVE ANALYSIS OF

GROUP I CATIONS
INTRODUCTION

QUALITATIVE ANALYSIS
- A method used for identification of ions or compounds in a sample. It primarily involves the separation of ions or
compounds in a mixture. Qualitative analysis employs both ion precipitation reactions (solubility tests) and
chemical reactivity tests. The separation of ions is easily achieved by taking advantage of their solubility
properties.

GROUP 1 CATIONS

The systematic analysis of the common cations is based upon the successive precipitation of groups of ions, so that the
total number of ions can be broken down into a small number of groups, each containing a number of related cations.
Group I cations are composed of those common cations whose chlorides are relatively insoluble in dilute acids.
Please READ Chapter 12: Group 1 Cations (Qualitative Analysis by E.S Gilreath pp.185-189)

At the end of this activity, the student should be able to:

1. Identify the principles involved in the qualitative analysis of cations.
2. Describe the principles involved in the separation and identification of Group 1 cations.
3. Understand chemical reactions involved in the analysis of Group 1 cations.
4. Appreciate the intricate process of qualitative analysis.

The successful separation of a group of cations is determined by the relative solubility products of the compounds formed
by the cations with the precipitating anion. Enumerate all the insoluble chlorides of Group I cation with their solubility
product constants.

Insoluble Chloride Solubility Product Constant

From the data above, compare then describe their solubility products and whether they are completely or incompletely
precipitated.

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 10 drops of Test
Solution

The original test solution may contain Chlorides of

Group I cation or oxychlorides of Antimony and Bismuth.
(+) 4 drops of 3F
Addition of Hydrochloric Acid causes the dissolution of the
HCl
latter; thereby, leaving the chlorides of Group I cation for
individual analysis.
Mix

Centrifuge

(+) 1 drop of 3F Slight excess of HCl not only causes a more complete
HCl precipitation of the chlorides of Group I cation, but also
prevents the formation of BiOCl and SbOCl.

Centrifuge

Separate

Centrifugate Precipitate

Wash

Lead Chloride may dissolve during the

Contains Group II-V 10 drops of cold
washing process. The addition of HCl
Cations water with 1 drop of
reduces its solubility by common-ion
*for further analysis 3F HCl
effect.

Centrifuge

Discard wash water White Precipitate

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 White precipitate (From Procedure 1) may be PbCl2, AgCl, and Hg2Cl2.

(+) 6-7 drops of

distilled water

Stir

Heat for 3 minutes

Centrifuge QUICKLY When separating keep the mixture hot in a water

bath, Why?
Separate

Centrifugate Precipitate

(+) 4 drops of 1F (+) 10 drops of

K2CrO4 NH3

Stir

Yellow precipitate Centrifuge

confirms the presence
of LEAD ION
Separate

Centrifugate Precipitate

Wash
Test for
(+) 3 F HNO3 (+) 10 drops of
acidity using Discard washing
until acidic water
litmus paper.

White precipitate (+) 2 drops

confirms the presence conc. HNO3
of SILVER ION

If the solution is not clear,

(+) 5 drops of
centrifuge then retain the
Distilled water
centrifugate.

(+) 1-2 drops of

SnCl2 solution

White/gray precipitate
confirms the presence
of MERCUROUS ION
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On the initial Addition of 3 F Hydrochloric Acid
The test solution may contain a white precipitate which could either be the chlorides of Group I or the
oxychlorides of Bismuth (Bi) and Antimony (Sb). Both can be precipitated;
however, the addition of concentrated Hydrochloric acid (HCl) can
differentiate the two. The oxychlorides of Bi and Sb will dissolve, whereas NOTE:
the chlorides of Group I will not. The reaction is reversible and the
presence of oxychloride
precipitate depends on the
BiOCl + 2H3O + Bi + Cl + 3H2O
3+ -

Bismuth Hydronium Bismuth Chlorine Water concentration of Hydronium ions.

Oxychloride Ion

On the Addition of EXCESS Hydrochloric Acid

Apart from ensuring that the precipitation of Group I cation is
complete, by virtue of common-ion effect, the excess prevents the
formation of BiOCl and SbOCl.
A large concentration of HCl or
AgCl + 2Cl- AgCl3-
Chloride ion should be avoided, since
Silver Chloride Chloride ion Silver Trichloride
the chloride ion in high concentration
increases the solubility of the
precipitated chlorides. PbCl2 + 2Cl- PbCl4-
Lead Chloride Chloride ion Lead Tetrachloride

On the Addition of 3F Ammonia

If the ammoniacal solution is left in contact with the precipitate of Mercury (Hg) and Mercuric Amidochloride
(HgNH2Cl) for an appreciable length of time, the soluble silver complex ion may react with metallic Hg. Therefore, a
small concentration of Silver (Ag+) may not give the usual test for silver ion.

2Hg + 2Ag(NH3)2 + Hg2 2+ + 2Ag + 4NH3

Mercury Silver Diamine Mercurous ion Silver Ammonia

On the Addition of 3F Nitric acid

The solution must be acidified to convert the Ag(NH3)2 + to Silver Chloride (AgCl); otherwise, even though silver
ions are present, no precipitate will form.

On the remaining Precipitate after the Treatment of Ammonia

If mercurous ions are present, the residue left from the Ammonia (NH3) treatment must be black or greatly
discolored, because of the precipitation of colloidal mercury.

Hg2Cl2 + 2NH3 HgNH2Cl + Hg + NH4 + + Cl-

Mercury Ammonia Mercuric Mercury Ammonium Chloride
Chloride Amidochloride Ion Ion

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 CHEMICAL REACTIONS INVOLVED IN THE SEPARATION AND IDENTIFICATION OF CATIONS OF GROUP I

Group precipitation
Pb2+ + 2Cl- PbCl2

Lead, silver and mercurous ion give white precipitates

with the chloride ion in an acid solution. Ag+ + Cl- AgCl

Hg22+ + 2Cl- Hg2Cl2

Separation and Identification of Lead Ion

An incomplete separation of Lead Chloride (PbCl2) from

the group precipitate is affected with hot water. PbCl2 is Pb2+ + CrO4- PbCrO4
soluble to the extent of approximately 1 g/100 ml at room
temperature, and 3.34 g/ml at the temperature of boiling
water. The threefold increase insolubility is small, but sufficient NOTE:
to give a lead-ion concentration that can be detected with Lead Chromate is mush less soluble than Lead
chromate ions. Chloride

Treatment of Residue in Group I Analysis with Ammonia

When a mixture of Silver Chloride (AgCl) and Mercury

Chloride (HgCl2) is treated with Ammonia (NH3), the AgCl
AgCl + 2NH3 Ag(NH3)2 + Cl-
dissolves, leaving a black residue composed of mercury and
mercuric aminochloride.

Ammonia acts upon mercurous chloride to produce an internal redox reaction in which one mercurous ion is
produced and the other is oxidized to the mercuric state. Mercuric aminochloride is white and the finely divided mercury
is black. The blackening of the mixture is an identification test for the mercurous ion.

Hg2Cl2 + 2NH3 HgNH2Cl + Hg + NH4 + Cl-

Confirmation for the presence of Silver Ion

The centrifugate from the treatment of the Group I precipitate with ammonia contains Ag(NH 3)2+ and Cl- ions. If the
solution is made acidic with nitric acid (HNO3), the complex is destroyed and AgCl is reprecipitated.

Ag(NH3)2 + Cl- + 2H3O AgCl + 2NH4 + NH4 + 2H2O

Identification of Mercurous Ion

The residue from the treatment of mercurous chloride with ammonia is a mixture of Hg and HgNH 2Cl. Although the
production of black mixture is sufficient to indicate the presence of the mercurous ion, additional confirmation is
obtained by dissolving the mixture in nitric acid and testing with stannous chloride solution.

3Hg + 2NO3- + 8H3O+ 3Hg2+ + 2NO + 12H2O

2HgNH2Cl + 2NO3- + 4H3O- 2Hg2+ + N2 + 2NO + 2Cl- + 8H2O

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 In the presence of chloride ions, the mercuric ions tend to form the slightly dissociated mercuric chloride molecule,
HgCl2, or the complex ion, HgCl4-

Hg2+ + 2Cl- HgCl2 HgCl2 + 2Cl- HgCl4

- Low Concentration of Chloride ions - - High Concentration of Chloride ions -

Acid solutions containing HgCl2 and HgCl4- give precipitates with stannous ions. These precipitates may be white, gray,
or black, depending upon the relative concentrations of the reactants.

2HgCl2 + SnCl4- Hg2Cl2 + SnCl6-

2HgCl4 + SnCl4- Hg2Cl2 + SnCl6- + 4Cl-

Further addition of stannous chloride reduces white Hg 2Cl2 to black, finely divided mercury. Generally, a gray mixture
of Hg2Cl2 and Hg is obtained.

Hg2Cl2 + SnCl4- 2Hg + SnCl6-

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