Nonmetal Oxygen Compounds

Most nonmetals react with oxygen to form nonmetal oxides. Depending on the available oxidation states for the element, a variety of oxides might form. Fluorine will combine with oxygen to form fluorides such as OF₂, where the oxygen has a 2+-oxidation state.

Sulfur Oxygen Compounds

The two common oxides of sulfur are sulfur dioxide, SO₂, and sulfur trioxide, SO₃. The odor of burning sulfur comes from sulfur dioxide. Sulfur dioxide, shown in the figure below, occurs in volcanic gases and in the atmosphere near industrial plants that burn fuel containing sulfur compounds.

A ball-and-stick model shows a yellow atom labeled, “S,” bonded on either side to a red atom labeled, “O.” A pair of Lewis structures are shown connected by a double-headed arrow. The left Lewis structure shows a sulfur atom with one lone pair of electrons double bonded on the left to an oxygen atom with two lone pairs of electrons and single bonded on the right to an oxygen atom with three lone pairs of electrons. The right Lewis structure is a mirror image of the structure on the left.

This image shows the molecular structure (left) and resonance forms (right) of sulfur dioxide.

Commercial production of sulfur dioxide is from either burning sulfur or roasting sulfide ores such as ZnS, FeS₂, and Cu₂S in air. (Roasting, which forms the metal oxide, is the first step in the separation of many metals from their ores.) A convenient method for preparing sulfur dioxide in the laboratory is by the action of a strong acid on either sulfite salts containing the \({\text{SO}}_{3}{}^{2-}\) ion or hydrogen sulfite salts containing \({\text{HSO}}_{3}{}^{\text{−}}.\)

Sulfurous acid, H₂SO₃, forms first, but quickly decomposes into sulfur dioxide and water. Sulfur dioxide also forms when many reducing agents react with hot, concentrated sulfuric acid. Sulfur trioxide forms slowly when heating sulfur dioxide and oxygen together, and the reaction is exothermic:

\(2{\text{SO}}_{2}(g)+{\text{O}}_{2}(g)\;⟶\;2{\text{SO}}_{3}(g)\phantom{\rule{5em}{0ex}}\text{Δ}H\text{°}=-197.8\;\text{kJ}\)

Sulfur dioxide is a gas at room temperature, and the SO₂ molecule is bent. Sulfur trioxide melts at 17 °C and boils at 43 °C. In the vapor state, its molecules are single SO₃ units (shown in the figure below), but in the solid state, SO₃ exists in several polymeric forms.

A ball-and-stick model shows a yellow atom labeled, “S,” bonded to three red atoms labeled, “O.” Three Lewis structures are shown connected by double-headed arrows. The left Lewis structure shows a sulfur atom single bonded on the lower left and right to oxygen atoms with three lone pairs of electrons each. The sulfur atom is also double bonded above to an oxygen atom with two lone pairs of electrons. The middle and right Lewis structures are the same as the left, but show the double bonded oxygen in the lower left and lower right positions, respectively.

This image shows the structure (top) of sulfur trioxide in the gas phase and its resonance forms (bottom).

The sulfur oxides react as Lewis acids with many oxides and hydroxides in Lewis acid-base reactions, with the formation of sulfites or hydrogen sulfites, and sulfates or hydrogen sulfates, respectively.

Halogen Oxygen Compounds

The halogens do not react directly with oxygen, but it is possible to prepare binary oxygen-halogen compounds by the reactions of the halogens with oxygen-containing compounds. Oxygen compounds with chlorine, bromine, and iodine are oxides because oxygen is the more electronegative element in these compounds. On the other hand, fluorine compounds with oxygen are fluorides because fluorine is the more electronegative element.

As a class, the oxides are extremely reactive and unstable, and their chemistry has little practical importance. Dichlorine oxide, formally called dichlorine monoxide, and chlorine dioxide, both shown in the figure below, are the only commercially important compounds. They are important as bleaching agents (for use with pulp and flour) and for water treatment.

Two space filling models are shown and labeled, “a,” and “b.” Model a shows a red atom labeled, “O,” bonded to two green atoms labeled, “C l,” in a v-shape. Model b shows a green atom labeled, “C l,” bonded to two red atoms labeled, “O,” in a v-shape.

This image shows the structures of the (a) Cl₂O and (b) ClO₂ molecules.

Nonmetal Oxygen Compounds