Chemistry » Metals, Metalloids, and Nonmetals » Occurrence, Preparation, and Properties of Halogens

Halides of the Representative Metals

Halides of the Representative Metals

Thousands of salts of the representative metals have been prepared. The binary halides are an important subclass of salts. A salt is an ionic compound composed of cations and anions, other than hydroxide or oxide ions. In general, it is possible to prepare these salts from the metals or from oxides, hydroxides, or carbonates. We will illustrate the general types of reactions for preparing salts through reactions used to prepare binary halides.

The binary compounds of a metal with the halogens are the halides. Most binary halides are ionic. However, mercury, the elements of group 13 with oxidation states of 3+, tin(IV), and lead(IV) form covalent binary halides.

The direct reaction of a metal and a halogen produce the halide of the metal. Examples of these oxidation-reduction reactions include:

\(\text{Cd}(s)+{\text{Cl}}_{2}(g)\;⟶\;{\text{CdCl}}_{2}(s)\)

\(\text{2Ga}(l)+3{\text{Br}}_{2}(l)\;⟶\;2{\text{GaBr}}_{3}(s)\)

Optional Video:

Reactions of the alkali metals with elemental halogens are very exothermic and often quite violent. Under controlled conditions, they provide exciting demonstrations for budding students of chemistry. You can view the initial heating of the sodium that removes the coating of sodium hydroxide, sodium peroxide, and residual mineral oil

If a metal can exhibit two oxidation states, it may be necessary to control the stoichiometry in order to obtain the halide with the lower oxidation state. For example, preparation of tin(II) chloride requires a 1:1 ratio of Sn to Cl2, whereas preparation of tin(IV) chloride requires a 1:2 ratio:

\(\text{Sn}(s)+{\text{Cl}}_{2}(g)\;⟶\;{\text{SnCl}}_{2}(s)\)

\(\text{Sn}(s)+2{\text{Cl}}_{2}(g)\;⟶\;{\text{SnCl}}_{4}(l)\)

The active representative metals—those that are easier to oxidize than hydrogen—react with gaseous hydrogen halides to produce metal halides and hydrogen. The reaction of zinc with hydrogen fluoride is:

\(\text{Zn}(s)+\text{2HF}(g)\;⟶\;{\text{ZnF}}_{2}(s)+{\text{H}}_{2}(g)\)

The active representative metals also react with solutions of hydrogen halides to form hydrogen and solutions of the corresponding halides. Examples of such reactions include:

\(\text{Cd}(s)+\text{2HBr}(aq)\;⟶\;{\text{CdBr}}_{2}(aq)+{\text{H}}_{2}(g)\)

\(\text{Sn}(s)+\text{2HI}(aq)\;⟶\;{\text{SnI}}_{2}(aq)+{\text{H}}_{2}(g)\)

Hydroxides, carbonates, and some oxides react with solutions of the hydrogen halides to form solutions of halide salts. It is possible to prepare additional salts by the reaction of these hydroxides, carbonates, and oxides with aqueous solution of other acids:

\({\text{CaCo}}_{3}(s)+\text{2HCl}(aq)\;⟶\;{\text{CaCl}}_{2}(aq)+{\text{CO}}_{2}(g)+{\text{H}}_{2}\text{O}(l)\)

\(\text{TlOH}(aq)+\text{HF}(aq)\;⟶\;\text{TlF}(aq)+{\text{H}}_{2}\text{O}(l)\)

A few halides and many of the other salts of the representative metals are insoluble. It is possible to prepare these soluble salts by metathesis reactions that occur when solutions of soluble salts are mixed (see the figure below). Metathesis reactions are examined in the tutorial on the stoichiometry of chemical reactions.

This figure shows three bottles and one bowl. All the bottles have lids. The first bottle is filled with a clear liquid. The second bottle is filled with a similarly clear liquid, but only about three-quarters of the way. The third bottle contains a red or pink liquid. The bowl contains a red or pink solid.

Solid HgI2 forms when solutions of KI and Hg(NO3)2 are mixed. (credit: Sahar Atwa)

Several halides occur in large quantities in nature. The ocean and underground brines contain many halides. For example, magnesium chloride in the ocean is the source of magnesium ions used in the production of magnesium. Large underground deposits of sodium chloride, like the salt mine shown in the figure below, occur in many parts of the world. These deposits serve as the source of sodium and chlorine in almost all other compounds containing these elements. The chlor-alkali process is one example.

A photograph of a mine shaft is shown.

Underground deposits of sodium chloride are found throughout the world and are often mined. This is a tunnel in the Kłodawa salt mine in Poland. (credit: Jarek Zok)

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