7

Ionic Compounds

As you have learned, ions are atoms or molecules bearing an electrical charge. A cation (a positive ion) forms when a neutral atom loses one or more electrons from its valence shell, and an anion (a negative ion) forms when a neutral atom gains one or more electrons in its valence shell.

Compounds composed of ions are called ionic compounds (or salts). The ions are held together by ionic bonds: electrostatic forces of attraction between oppositely charged cations and anions. The properties of ionic compounds shed some light on the nature of ionic bonds. Ionic solids exhibit a crystalline structure and tend to be rigid and brittle. They also tend to have high melting and boiling points, which suggests that ionic bonds are very strong. Ionic solids are also poor conductors of electricity for the same reason—the strength of ionic bonds prevents ions from moving freely in the solid state. Most ionic solids, however, dissolve readily in water. Once dissolved or melted (two different processes), ionic compounds are excellent conductors of electricity and heat because the ions can move about freely.

Neutral atoms and their associated ions have very different physical and chemical properties. Sodium atoms form sodium metal, a soft, silvery-white metal that burns vigorously in air and reacts explosively with water. Chlorine atoms form chlorine gas, Cl2, a yellow-green gas that is extremely corrosive to most metals and very poisonous to animals and plants. The vigorous reaction between the elements sodium and chlorine forms the white, crystalline compound sodium chloride, common table salt, which contains sodium cations and chloride anions, Figure 1. The compound composed of these ions exhibits properties entirely different from the properties of the elements sodium and chlorine. Chlorine is poisonous, but sodium chloride is essential to life; sodium atoms react vigorously with water, but sodium chloride simply dissolves in water.

Three pictures are shown and labeled “a,” “b,” and “c,” from left to right. Image a shows a glass jar with a lid that is full of a clear, colorless liquid in which a silver solid is suspended. Image b depicts a glass bottle with a blue lid that is full of a yellow-green gas. Image c shows a black dish that is full of a white, crystalline solid.
(a) Sodium is a soft metal that must be stored in mineral oil to prevent reacting with air or water. (b) Chlorine is a pale yellow-green poisonous gas. (c) When combined, they form white crystals of sodium chloride (table salt). (credit a: modification of work by “Jurii”/Wikimedia Commons)

The Formation of Ionic Compounds

Binary ionic compounds are composed of just two elements: a metal (which forms the cations) and a nonmetal (which forms the anions). For example, NaCl is a binary ionic compound. We can think about the formation of such compounds in terms of the periodic properties of the elements. Many metallic elements have relatively low ionization potentials and lose electrons easily. These elements lie to the left in a period or near the bottom of a group on the periodic table. Nonmetal atoms have relatively high electron affinities and thus readily gain electrons lost by metal atoms, thereby filling their valence shells. Nonmetallic elements are found in the upper-right corner of the periodic table.

As all substances must be electrically neutral, the total number of positive charges on the cations of an ionic compound must equal the total number of negative charges on its anions. The formula of an ionic compound represents the simplest ratio of the numbers of ions necessary to give identical numbers of positive and negative charges. For example, the formula for aluminum oxide, Al2O3, indicates that this ionic compound contains two aluminum cations, Al3+, for every three oxide anions, O2− [thus, (2 × +3) + (3 × –2) = 0].

It is important to note, however, that the formula for an ionic compound does not represent the physical arrangement of its ions. It is incorrect to refer to a sodium chloride (NaCl) as a “molecule” because there is not a single ionic bond, per se, between any specific pair of sodium and chloride ions. The attractive forces between ions are isotropic—the same in all directions—meaning that any particular ion is equally attracted to all of the nearby ions of opposite charge. This results in the ions arranging themselves into a tightly bound, three-dimensional lattice structure. Sodium chloride, for example, consists of a regular arrangement of equal numbers of Na+ cations and Cl anions (Figure 2).

Two diagrams are shown and labeled “a” and “b.” Diagram a shows a cube made up of twenty-seven alternating purple and green spheres. The purple spheres are smaller than the green spheres. Diagram b shows the same spheres, but this time, they are spread out and connected in three dimensions by white rods. The purple spheres are labeled “N superscript postive sign” while the green are labeled “C l superscript negative sign.”The atoms in sodium chloride (common table salt) are arranged to (a) maximize opposite charges interacting. The smaller spheres represent sodium ions, the larger ones represent chloride ions. In the expanded view (b), the geometry can be seen more clearly. Note that each ion is “bonded” to all of the surrounding ions—six in this case.

The strong electrostatic attraction between Na+ and Cl ions holds them tightly together in solid NaCl. It requires 769 kJ of energy to dissociate one mole of solid NaCl into separate gaseous Na+ and Cl ions:

NaCl(s) → Na+(g) + Cl(g)        \Delta H = \SI{769}{kJ}

Covalent Compounds

Ionic bonding results from the electrostatic attraction of oppositely charged ions that are typically produced by the transfer of electrons between metallic and nonmetallic atoms. A different type of bonding results from the mutual attraction of atoms for a “shared” pair of electrons. Such bonds are called covalent bonds. Covalent bonds are formed between two atoms when both have similar tendencies to attract electrons to themselves (i.e., when both atoms have identical or fairly similar ionization energies and electron affinities). For example, two hydrogen atoms bond covalently to form an H2 molecule; each hydrogen atom in the Hmolecule has two electrons stabilizing it, giving each atom the same number of valence electrons as the noble gas He.

Compounds that contain covalent bonds exhibit different physical properties than ionic compounds. Because the attraction between molecules, which are electrically neutral, is weaker than that between electrically charged ions, covalent compounds generally have much lower melting and boiling points than ionic compounds. In fact, many covalent compounds are liquids or gases at room temperature and, in their solid states, they are typically much softer than ionic solids. Furthermore, whereas ionic compounds are good conductors of electricity when dissolved in water, most covalent compounds are insoluble in water; since they are electrically neutral, they are poor conductors of electricity in any state.

Key Concepts and Summary

Atoms gain or lose electrons to form ions with particularly stable electron configurations. The charges of cations formed by the representative metals may be determined readily because, with few exceptions, the electronic structures of these ions have either a noble gas configuration or a completely filled electron shell. The charges of anions formed by the nonmetals may also be readily determined because these ions form when nonmetal atoms gain enough electrons to fill their valence shells.

Chemistry End of Chapter Exercises

1. Does a cation gain protons to form a positive charge or does it lose electrons?

2. Iron(III) sulfate [Fe2(SO4)3] is composed of Fe3+ and SO42- ions. Explain why a sample of iron(III) sulfate is uncharged.

3. Which of the following atoms would be expected to form negative ions in binary ionic compounds and which would be expected to form positive ions: P, I, Mg, Cl, In, Cs, O, Pb, Co?

4. Which of the following atoms would be expected to form negative ions in binary ionic compounds and which would be expected to form positive ions: Br, Ca, Na, N, F, Al, Sn, S, Cd?

5. Predict the charge on the monatomic ions formed from the following atoms in binary ionic compounds:

(a) P

(b) Mg

(c) Al

(d) O

(e) Cl

(f) Cs

6. Predict the charge on the monatomic ions formed from the following atoms in binary ionic compounds:

(a) I

(b) Sr

(c) K

(d) N

(e) S

(f) In

 

7. Using the periodic table, predict whether the following chlorides are ionic or covalent: KCl, NCl3, ICl, MgCl2, PCl5, and CCl4.

8. Using the periodic table, predict whether the following chlorides are ionic or covalent: SiCl4, PCl3, CaCl2, CsCl, CuCl2, and CrCl3.

9. For each of the following compounds, state whether it is ionic or covalent. If it is ionic, write the symbols for the ions involved:

(a) NF3

(b) BaO

(c) (NH4)2CO3

(d) Sr(H2PO4)2

(e) IBr

(f) Na2O

10. For each of the following compounds, state whether it is ionic or covalent, and if it is ionic, write the symbols for the ions involved:

(a) KClO4

(b) Mg(C2H3O2)2

(c) H2S

(d) Ag2S

(e) N2Cl4

(f) Co(NO3)2

11. For each of the following pairs of ions, write the formula of the compound they will form:

(a) Ca2+, S2−

(b) NH4+, SO42−

(c) Al3+, Br

(d) Na+HPO42−

(e) Mg2+PO43−

12. For each of the following pairs of ions, write the formula of the compound they will form:

(a) K+, O2−

(b) Al3+, O2−

(c) Na+CO32−

(e) Ba2+PO43−

13. From the labels of several commercial products, prepare a list of six ionic compounds in the products. For each compound, write the formula. (You may need to look up some formulas in a suitable reference.)

Glossary

covalent bond
attractive force between the nuclei of a molecule’s atoms and pairs of electrons between the atoms
covalent compound
(also, molecular compound) composed of molecules formed by atoms of two or more different elements
inert pair effect
tendency of heavy atoms to form ions in which their valence s electrons are not lost

ionic bond
electrostatic forces of attraction between the oppositely charged ions of an ionic compound

ionic compound
compound composed of cations and anions combined in ratios, yielding an electrically neutral substance
molecular compound
(also, covalent compound) composed of molecules formed by atoms of two or more different elements
monatomic ion
ion composed of a single atom
oxyanion
polyatomic anion composed of a central atom bonded to oxygen atoms
polyatomic ion
ion composed of more than one atom

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