Predictable Charges

You can often use the periodic table to predict whether an atom will form an anion or a cation, and you can often predict the charge of the resulting ion. Atoms of many main-group (s and p block) metals lose enough electrons to leave them with the same number of electrons as an atom of the preceding noble gas. In other words, an atom of an alkali metal (group 1) loses one electron and forms a cation with a 1+ charge; an alkaline earth metal (group 2) loses two electrons and forms a cation with a 2+ charge, and so on. For example, a neutral calcium atom, with 20 protons and 20 electrons, loses two electrons. This results in a cation with 20 protons, 18 electrons, and a 2+ charge. It is symbolized Ca²⁺, and has the same number of electrons as atoms of the preceding noble gas, argon. The name of a metal ion is the same as the name of the metal atom from which it forms, so Ca²⁺ is called a calcium ion.

When atoms of nonmetal elements form ions, they generally gain enough electrons to give them the same number of electrons as an atom of the next noble gas in the periodic table. Atoms of group 17 gain one electron and form anions with a 1− charge; atoms of group 16 gain two electrons and form ions with a 2− charge, and so on. For example, the neutral bromine atom, with 35 protons and 35 electrons, can gain one electron. This results in an anion with 35 protons, 36 electrons, and a 1− charge. It is symbolized Br⁻, and has the same number of electrons as atoms of the next noble gas, krypton.

Moving from the far left to the right on the periodic table, main-group elements tend to form cations with a charge equal to the group number. That is, group 1 elements form 1+ ions; group 2 elements form 2+ ions, and so on. Moving from the far right to the left on the periodic table, elements often form anions with a negative charge equal to the number of groups moved left from the noble gases. For example, group 17 elements (one group left of the noble gases) form 1− ions; group 16 elements (two groups left) form 2− ions, and so on. This trend can be used as a guide in many cases, but its predictive value decreases when moving toward the center of the periodic table. In fact, transition metals and some other metals often exhibit variable charges that are not predictable by their location in the table. For example, copper can form ions with a 1+ or 2+ charge, and iron can form ions with a 2+ or 3+ charge.

Because an ionic compound is not made up of discrete molecules, it may not be properly symbolized using a molecular formula. Instead, ionic compounds are symbolized by a formula indicating the relative numbers of its constituent ions, using the simplest whole-number ratios. For compounds containing only monatomic ions (such as NaCl), these formulas are just the empirical formulas.

Naming Ionic Compounds

Compounds Containing Only Monatomic Ions

The name of a binary compound containing monatomic ions consists of the name of the cation (the name of the metal) followed by the name of the anion (the name of the nonmetallic element with its ending replaced by the suffix –ide). Some examples are given below.

Compounds Containing a Metal Ion with a Variable Charge

Most of the transition metals can form two or more cations with different charges. Compounds of these metals with nonmetals are named with the same method as above, except the charge of the metal ion is specified by a Roman numeral in parentheses after the name of the metal. The charge of the metal ion is determined from the formula of the compound and the charge of the anion. For example, consider binary ionic compounds of iron and chlorine. Iron typically exhibits a charge of either 2+ or 3+ (Figure 1), and the two corresponding compound formulas are FeCl₂ and FeCl₃. The simplest name, “iron chloride,” will, in this case, be ambiguous, as it does not distinguish between these two compounds. In cases like this, the charge of the metal ion is included as a Roman numeral in parentheses immediately following the metal name. These two compounds are then unambiguously named iron(II) chloride and iron(III) chloride, respectively. Other examples are provided below.

Out-of-date nomenclature used the suffixes –ic and –ous to designate metals with higher and lower charges, respectively: Iron(III) chloride, FeCl₃, was previously called ferric chloride, and iron(II) chloride, FeCl₂, was known as ferrous chloride. Though this naming convention has been largely abandoned by the scientific community, it remains in use by some segments of industry. For example, you may see the words stannous fluoride on a tube of toothpaste. This represents the formula SnF₂, which is more properly named tin(II) fluoride. The other fluoride of tin is SnF₄, which was previously called stannic fluoride but is now named tin(IV) fluoride.

Polyatomic Ions

The ions that we have discussed so far are called monatomic ions, that is, they are ions formed from only one atom. We also find many polyatomic ions. These ions, which act as discrete units, are electrically charged molecules (a group of covalently-bonded atoms with an overall charge). Oxyanions are polyatomic ions that contain one or more oxygen atoms. Table below lists some of the common polyatomic ions.

Note that there is a system for naming some polyatomic ions; -ate and -ite are suffixes designating polyatomic ions containing more or fewer oxygen atoms. Per- (short for “hyper” meaning “above”) and hypo- (meaning “under”) are prefixes meaning more oxygen atoms than -ate and fewer oxygen atoms than -ite, respectively. For example, perchlorate is ClO₄⁻, chlorate is ClO₃⁻, chlorite is ClO₂⁻ and hypochlorite is ClO⁻. Unfortunately, the number of oxygen atoms corresponding to a given suffix or prefix is not consistent; for example, nitrate is NO₃⁻ while sulfate is SO₄²⁻.

Naming Polyatomic Ions

Compounds containing polyatomic ions are named similarly to those containing only monatomic ions, except there is no need to change to an –ide ending, since the suffix is already present in the name of the anion. Examples are shown below.

Many ionic compounds contain polyatomic ions as the cation, the anion, or both. As with simple ionic compounds, these compounds must also be electrically neutral, so their formulas can be predicted by treating the polyatomic ions as discrete units. We use parentheses in a formula to indicate a group of atoms that behave as a unit. For example, the formula for calcium phosphate, one of the minerals in our bones, is Ca₃(PO₄)₂. This formula indicates that there are three calcium ions (Ca²⁺) for every two phosphate (PO₄³⁻) groups. The PO₄³⁻ groups are discrete units, each consisting of one phosphorus atom and four oxygen atoms, and having an overall charge of 3−. The compound is electrically neutral, and its formula shows a total count of three Ca, two P, and eight O atoms.

Because an ionic compound is not made up of single, discrete molecules, it may not be properly symbolized using a molecular formula. Instead, ionic compounds must be symbolized by a formula indicating the relative numbers of its constituent ions. For compounds containing only monatomic ions (such as NaCl) and for many compounds containing polyatomic ions (such as CaSO₄), these formulas are just the empirical formulas. However, the formulas for some ionic compounds containing polyatomic ions are not empirical formulas. For example, the ionic compound sodium oxalate is comprised of Na⁺ and C₂O₄²⁻ ions combined in a 2:1 ratio, and its formula is written as Na₂C₂O₄. The subscripts in this formula are not the smallest-possible whole numbers, as each can be divided by 2 to yield the empirical formula, NaCO₂. This, however, is not the accepted formula for sodium oxalate, as it does not accurately represent the compound’s polyatomic anion, C₂O₄²⁻.

Lattice Energy

The lattice energy of an ionic compound is a measure of the strength of the electrostatic attraction between its positive and negative ions. The lattice energy (ΔH_lattice) of an ionic compound is defined as the energy required to separate one mole of the solid into its component gaseous ions. For the ionic solid, MX, the lattice energy is the enthalpy change of the process:

MX(s)  →  Mⁿ⁺(g) + X^n-(g)        ΔH_lattice

Note that we are using the convention where the ionic solid is separated into ions, so our lattice energies will be endothermic (positive values). Some texts use the equivalent but opposite convention, defining lattice energy as the energy released when separate ions combine to form a lattice and giving negative (exothermic) values. Thus, if you are looking up lattice energies in another reference, be certain to check which definition is being used. In both cases, a larger magnitude for lattice energy indicates a more stable ionic compound. For sodium chloride, ΔH_lattice = 769 kJ/mol. Thus, it requires 769 kJ to separate one mole of solid NaCl into gaseous Na⁺ and Cl^– ions. When one mole each of gaseous Na⁺ and Cl^– ions form solid NaCl, 769 kJ of heat is released.

The lattice energy ΔH_lattice of an ionic crystal can be expressed by the following equation (derived from Coulomb’s law, governing the forces between electric charges):

ΔH_lattice =

in which C is a constant that depends on the type of crystal structure; Z⁺ and Z^– are the charges on the ions; and R_o is the interionic distance (the sum of the radii of the positive and negative ions). Thus, the lattice energy of an ionic crystal increases rapidly as the charges of the ions increase and the sizes of the ions decrease. When all other parameters are kept constant, doubling the charge of both the cation and anion quadruples the lattice energy. For example, the lattice energy of LiF (Z⁺ and Z^– = 1) is 1023 kJ/mol, whereas that of MgO (Z⁺ and Z^– = 2) is 3900 kJ/mol (R_o is nearly the same—about 200 pm for both compounds).

Different interatomic distances produce different lattice energies. For example, we can compare the lattice energy of MgF₂ (2957 kJ/mol) to that of MgI₂ (2327 kJ/mol) to observe the effect on lattice energy of the smaller ionic size of F^– as compared to I^–.