CHAPTER II

SUMMARY OF THE BOOKS

A. The Book’s Identity

BOOK 1
Title : Analytical Chemistry ( Volume I Qualitative Analysis
Title of the chapter : Reaction of the metals (cation) in group II and Group III
Name of author : Hall W.T
Publisher : JOHN WILEY AND SONS, Inc, New York
Publish date : 1916
Number of pages : 125-516

B. Summary
Anions are commonly known as negative ions, usually anions are found from residual acids,
anions are usually present to stabilize cations. NO3-, NO2-, CH3COO-, SO42-, CO32-, NO2-,
AsO43-, I-, and Br- are some examples of anions that are often used in chemical analysis, to
identify their existence, then qualitative chemical analysis is used . Cation is commonly known as
a positive ion. Na +, K +, Ca2 + are some examples of cations that are often used in chemical
analysis.
Identifying anions and cations can be done by:
1. Change color
2. Smell
3. Solubility and Ksp (sediment)
4. Gas bubbles
5. Acid-base, redox, complex reactions
2.3 Introduction of Cation Element Group I
Group I cations or also called Chloride group cations which consist of: Pb2 +, Hg +, Ag +. This
cation forms deposits with dilute HCl. These deposits are PbCl2, Hg2Cl2 and AgCl which are all
white.
To ascertain whether the deposits contain only one cation, two cations or three cations are then
followed by separation and identification of group I cations. Group I cations form deposits with
dilute hydrochloric acid. The deposits that occur are all white. These group ions are lead,
mercurium (I) or mercury, and silver.
In systematic qualitative analysis, cations are classified into five groups, based on the cation
characteristics there are several reagents. Reagents that are commonly used include: hydrochloric
acid, hydrogen sulfide, ammonium sulfide, and ammonium carbonate. Cation classification is
based on whether a cation reacts with reagents, these reagents by forming deposits or not. it can
be said that the most common cation classification is based on differences in solubility of
chlorides, sulfides, and carbonates from these cations. Reagents used for the most common
cation classifications are:
1. HCl
2. H2S
3. (NH4) 2S
4. (NH4) 2CO3
This classification is based on whether a cation reacts with these reagents by forming deposits or
not. The most common cation classifications are based on differences in solubility of chlorides,
sulfates and carbonates from these cations.
The five categories of cations and the characteristics of these groups are as follows:

Group I cations: Lead (II), Merkurium (I), and Silver (I)

Group reagents: Dilute hydrochloric acid (2M)
Group reaction: White lead chloride deposits (PbCl2), Mercurium (I) chloride (Hg2Cl2), and
silver chloride (AgCl)
Group I cations form insoluble chlorides, but lead chloride is slightly soluble in water,
and therefore lead never settles perfectly if dilute hydrochloric acid is added to a remaining lead
ion sample which is deposited quantitatively with H2S in a joint acidic atmosphere Group II
cation Nitrates from group I cations are very soluble between sulfates, lead is practically
insoluble, while silver sulfate is much more. Solubility of mercurium (I) sulfate is located
between the two substances above.
Bromides and iodides also do not dissolve. While the deposition of lead halide is not perfect and
the sediment is easily dissolved in hot water. Sulfide is insoluble, acetate-acetate is more soluble,
although silver acetate can precipitate from a slightly concentrated solution. Hydroxides and
carbonates will be deposited with equivalent reagents, but in excess reagents, they can move in a
variety of ways where there is a difference in the properties of this substance to ammonia.
Group Cation I: Timbel (II), Mercurium (I), and Silver (I)
The cations in the first group form insoluble chlorides. But chloride lead is slightly soluble in
water so it never settles perfectly when dilute hydrochloric acid is added to a sample; the
remaining lead ions are deposited quantitatively with hydrogen sulfide in an acidic atmosphere
with the second cation.

1.1 Lead (Pb)

Lead is metallic gray metal with density of 11.48 g / ml at room temperature. Lead is
easily dissolved in moderate concentrations of nitric acid (8M), and nitrogen oxides are formed:
3Pb + 8HNO3 → 3Pb2 + 6NO3- + 2NO + 4H2O
Colorless nitrogen (II) oxide gas when mixed with air will be oxidized to red colored nitrogen
dioxide:
2NO (colorless) + O2 → 2NO2 (red)
With concentrated nitric acid a protective layer of nitric lead can form on a metal surface which
prevents further dissolution. Reactions of lead ion (II)
Dilute hydrochloric acid
Hydrogen sulfide in a neutral or dilute acid atmosphere: sulfide lead black deposits
Ammonia solution
Sodium hydroxide

1.2 Mercurium or Mercury (Hg)

Mercurium is a silvery white liquid metal at ordinary temperatures with a density of
13.534 g / ml at 25 ℃. Mercurium is easy to react with nitric acid, but is not affected by
hydrochloric acid or dilute sulfuric acid (2M).
Reactions of the mercurium (I) ion
Dilute hydrochloric acid or dissolved chlorides: white deposits of mercurium (I) chloride
(calomel)
Hydrogen sulfide in a neutral or aqueous atmosphere: black precipitate, which is a mixture of
mercurium (II) sulfide and metallic mercury
Ammonia solution: black precipitate which is a metal mixture of mercurium and mercurium (II)
alkaline amidonitrate.
Sodium hydroxide: black precipitate of mercurium (I) oxide

1.3 Perak, (Ag)

Silver is a white, forged, clay-colored metal with a density of 10.5g / ml and melting at
960.5 ℃. Silver is insoluble in hydrochloric acid, dilute sulfuric acid (1M) or dilute nitric acid
(2M). In more concentrated nitric acid (8M) or in hot concentrated acids, silver dissolves:
6Ag + 8 HNO3 → 6Ag ++ 2NO + 6NO3- + 4H2O
2Ag + 2H2SO4 → 2Ag + + SO42- + SO2 + 2H2O
Silver (I) ion reactions:
Dilute hydrochloric acid (or dissolved chlorides): white silver chloride deposits.
Hydrogen sulfide (gas or saturated water solution) in a neutral or acidic atmosphere: black silver
sulfide deposits
Ammonia solution: silver oxide brown precipitate
Sodium hydroxide: silver oxide brown precipitate

Group cation II: Mercurium (II), Timbel (II), Bismut (III), Copper (II), Cadmium (II),
Arsenic (III) and (V), Stibium (III) and (V), and Tin ( II) and (IV).

2.1 Mercurium (Mercury), Hg-Merkurium (II)

Reactions of mercurium (II) ions:
Hydrogen Sulfide (gas or saturated water solution): white deposits of mercurium (II)
chlorosulfide are formed due to the presence of dilute hydrochloric acid. When hydrogen sulfide
is added further a black precipitate of mercurium (II) sulfide will be formed.
Ammonia solution: white precipitate with mixed composition, basically from mercurium (II)
oxide and mercurium (II) amidonitrate:
2Hg2 + + NO3- + 4NH3 + H2O HgO.Hg (NH2) NO3 + 3NH4 +
Sodium hydroxide when added in small amounts: red-brown precipitate with different
compositions, if added to the amount of thoichiometrics the precipitate turns yellow when
mercurium (II) oxide is formed:
Hg2 + + 2OH- HgO + H2O
Potassium Cyanide (POISON): There is no change in the dilute solution (difference from other
ions of the copper sub-group)
Copper sheets or currencies reduce mercurium (II) ions to metal:
Cu + Hg2 + Cu2 + + Hg

2.2 Bismuth (Bi)

Bismuth is a reddish-white, crystalline, brittle metal and has a melting point of 271.5oC. Bismuth
is insoluble in hydrochloric acid but can dissolve in oxidizing acids such as concentrated nitric
acid, king water, or concentrated sulfuric acid. Bismuth (III) ion reactions
Hydrogen sulfide (saturated water solution gas): bismuth sulfide black precipitate
Ammonia solution: white base salt with various compositions.
Sodium hydroxide: white deposits of bismuth (III) hydroxide
Potassium cyanide (POISON): white precipitate, bismuth hydroxide. This reaction is hydrolysis:
Bi3 + + 3H2O + 3CN- Bi (OH) 3 + 3HCN

2.3 Copper (Cu)

Copper is a pink, soft, forged and clay metal. Copper has a melting point of 1038oC. Copper is
insoluble in dilute hydrochloric acid and sulfuric acid, but can be slightly soluble in the presence
of oxygen. Reactions of copper (II) ions:
Hydrogen sulfide (gas or saturated water solution): black deposits, copper (II) sulfide
Ammonia solution when added in very small amounts: blue precipitate an alkaline salt (base
copper sulfate).
Sodium hydroxide in cold solution: blue copper (II) hydroxide deposits.
Potassium iodide: precipitates white copper (I) iodide, but the solution is dark brown because of
the formation of tri-iodide (iodine) ions.
Potassium Cyanide (POISON): A precipitate of yellow copper (II) cyanide is formed if very little
is added.
2.4. Cadmium (Cd)
Cadmium is a silvery white metal that can be forged and clay. Cadmium has a melting point at
321oC and dissolves slowly in dilute acid by releasing hydrogen.
Cd + 2H + Cd2 ++ H2
Cadmium (II) ion reactions:
Hydrogen sulfide (gas or saturated water solution): yellow cadmium sulfide precipitate
Ammonia solution when added dropwise: white deposits of cadmium (II) hydroxide
Sodium hydroxide: white precipitate of cadmium (II) hydroxide
Potassium cyanide (POISON): white deposits of cadmium cyanide
Potassium thiocyanate: does not form deposits (difference from copper)
Potassium iodide: does not form deposits (difference from copper)
2.5 Arsenic (III)
Arsenic is a gray solid like steel, brittle, and has a knot like metal. Arsenic is sublimated
and smells like garlic when heated. Reactions of arsenic (III) ions
Hydrogen sulfide: deposits of yellow arsenic (III) sulfide
Silver nitrate: yellow silver arsenite deposits in neutral solution (different from arsenate)
Copper sulfate solution: precipitated green copper arsenite (Scheele green)
Potassium tri-iodide (iodine solution in potassium iodide): oxidizes ionarshenite while losing
color
2.6. Arsenic (V)
Arsenic ion reactions:
Hydrogen sulfide: precipitate does not occur immediately in the presence of chloride acid.
Silver nitrate solution: brownish red precipitate, Ag3AsO4 silver arsenate from neutral solution.
The precipitate is soluble in acid and in ammonia solution it remains insoluble in acetic acid.
2.7 Stibium (III)
Stibium is a glossy silvery white metal that has a melting point 630 ℃. Stibium is
insoluble in hydrochloric acid and dilute sulfuric acid. Compound-Stibium (V) compounds
contain antimonate ions, SbO43-. Its characteristics are similar with its equivalent arsenic
compounds.

1.Advantages
a) Has a broad explanation of the identification of types of cations in groups 2 and 3
b) Use analysis translation when adding reagents for identification
c) Good introduction of each substance contained in each group.
 d) Has an explanation and several ways to identify cations
2.Disadvantages
a) Books have been published long ago which have enabled a much better way to
identify cations
b) The book does not provide an identification scheme for each cations.

Hall, W.T.,(1903), Analytical Chemistry, John Willey and Sons Inc, New York.