# Representative Metals, Metalloids, and Nonmetals

## Structure and General Properties of the Metalloids

A series of six elements called the metalloids separate the metals from the nonmetals in the periodic table. The metalloids are boron, silicon, germanium, arsenic, antimony, and tellurium. These elements look metallic; however, they do not conduct electricity as well as metals so they are semiconductors. They are semiconductors because their electrons are more tightly bound to their nuclei than are those of metallic conductors. Their chemical behavior falls between that of metals and nonmetals. For example, the pure metalloids form covalent crystals like the nonmetals, but like the metals, they generally do not form monatomic anions. This intermediate behavior is in part due to their intermediate electronegativity values. In this section, we will briefly discuss the chemical behavior of metalloids and deal with two of these elements—boron and silicon—in more detail.
The metalloid boron exhibits many similarities to its neighbor carbon and its diagonal neighbor silicon. All three elements form covalent compounds. However, boron has one distinct difference in that its 2s22p1 outer electron structure gives it one less valence electron than it has valence orbitals. Although boron exhibits an oxidation state of 3+ in most of its stable compounds, this electron deficiency provides boron with the ability to form other, sometimes fractional, oxidation states, which occur, for example, in the boron hydrides.
Silicon has the valence shell electron configuration 3s23p2, and it commonly forms tetrahedral structures in which it is sp3 hybridized with a formal oxidation state of 4+. The major differences between the chemistry of carbon and silicon result from the relative strength of the carbon-carbon bond, carbon’s ability to form stable bonds to itself, and the presence of the empty 3d valence-shell orbitals in silicon. Silicon’s empty d orbitals and boron’s empty p orbital enable tetrahedral silicon compounds and trigonal planar boron compounds to act as Lewis acids. Carbon, on the other hand, has no available valence shell orbitals; tetrahedral carbon compounds cannot act as Lewis acids. Germanium is very similar to silicon in its chemical behavior.
Arsenic and antimony generally form compounds in which an oxidation state of 3+ or 5+ is exhibited; however, arsenic can form arsenides with an oxidation state of 3−. These elements tarnish only slightly in dry air but readily oxidize when warmed.
Tellurium combines directly with most elements. The most stable tellurium compounds are the tellurides—salts of Te2− formed with active metals and lanthanides—and compounds with oxygen, fluorine, and chlorine, in which tellurium normally exhibits an oxidation state 2+ or 4+. Although tellurium(VI) compounds are known (for example, TeF6), there is a marked resistance to oxidation to this maximum group oxidation state.

### Structures of the Metalloids

Covalent bonding is the key to the crystal structures of the metalloids. In this regard, these elements resemble nonmetals in their behavior.
Elemental silicon, germanium, arsenic, antimony, and tellurium are lustrous, metallic-looking solids. Silicon and germanium crystallize with a diamond structure. Each atom within the crystal has covalent bonds to four neighboring atoms at the corners of a regular tetrahedron. Single crystals of silicon and germanium are giant, three-dimensional molecules. There are several allotropes of arsenic with the most stable being layer like and containing puckered sheets of arsenic atoms. Each arsenic atom forms covalent bonds to three other atoms within the sheet. The crystal structure of antimony is similar to that of arsenic, both shown in . The structures of arsenic and antimony are similar to the structure of graphite, covered later in this chapter. Tellurium forms crystals that contain infinite spiral chains of tellurium atoms. Each atom in the chain bonds to two other atoms.
Pure crystalline boron is transparent. The crystals consist of icosahedra, as shown in , with a boron atom at each corner. In the most common form of boron, the icosahedra pack together in a manner similar to the cubic closest packing of spheres. All boron-boron bonds within each icosahedron are identical and are approximately 176 pm in length. In the different forms of boron, there are different arrangements and connections between the icosahedra.
The name silicon is derived from the Latin word for flint, silex. The metalloid silicon readily forms compounds containing Si-O-Si bonds, which are of prime importance in the mineral world. This bonding capability is in contrast to the nonmetal carbon, whose ability to form carbon-carbon bonds gives it prime importance in the plant and animal worlds.

### Occurrence, Preparation, and Compounds of Boron and Silicon

Boron constitutes less than 0.001% by weight of the earth’s crust. In nature, it only occurs in compounds with oxygen. Boron is widely distributed in volcanic regions as boric acid, B(OH)3, and in dry lake regions, including the desert areas of California, as borates and salts of boron oxyacids, such as borax, Na2B4O7⋅10H2O.
Elemental boron is chemically inert at room temperature, reacting with only fluorine and oxygen to form boron trifluoride, BF3, and boric oxide, B2O3, respectively. At higher temperatures, boron reacts with all nonmetals, except tellurium and the noble gases, and with nearly all metals; it oxidizes to B2O3 when heated with concentrated nitric or sulfuric acid. Boron does not react with nonoxidizing acids. Many boron compounds react readily with water to give boric acid, B(OH)3 (sometimes written as H3BO3).
Reduction of boric oxide with magnesium powder forms boron (95–98.5% pure) as a brown, amorphous powder:
An amorphous substance is a material that appears to be a solid, but does not have a long-range order like a true solid. Treatment with hydrochloric acid removes the magnesium oxide. Further purification of the boron begins with conversion of the impure boron into boron trichloride. The next step is to heat a mixture of boron trichloride and hydrogen:
Silicon makes up nearly one-fourth of the mass of the earth’s crust—second in abundance only to oxygen. The crust is composed almost entirely of minerals in which the silicon atoms are at the center of the silicon-oxygen tetrahedron, which connect in a variety of ways to produce, among other things, chains, layers, and three-dimensional frameworks. These minerals constitute the bulk of most common rocks, soil, and clays. In addition, materials such as bricks, ceramics, and glasses contain silicon compounds.
It is possible to produce silicon by the high-temperature reduction of silicon dioxide with strong reducing agents, such as carbon and magnesium:
Extremely pure silicon is necessary for the manufacture of semiconductor electronic devices. This process begins with the conversion of impure silicon into silicon tetrahalides, or silane (SiH4), followed by decomposition at high temperatures. Zone refining, illustrated in , completes the purification. In this method, a rod of silicon is heated at one end by a heat source that produces a thin cross-section of molten silicon. Slowly lowering the rod through the heat source moves the molten zone from one end of the rod to other. As this thin, molten region moves, impurities in the silicon dissolve in the liquid silicon and move with the molten region. Ultimately, the impurities move to one end of the rod, which is then cut off.
This highly purified silicon, containing no more than one part impurity per million parts of silicon, is the most important element in the computer industry. Pure silicon is necessary in semiconductor electronic devices such as transistors, computer chips, and solar cells.
Like some metals, passivation of silicon occurs due the formation of a very thin film of oxide (primarily silicon dioxide, SiO2). Silicon dioxide is soluble in hot aqueous base; thus, strong bases destroy the passivation. Removal of the passivation layer allows the base to dissolve the silicon, forming hydrogen gas and silicate anions. For example:
Silicon reacts with halogens at high temperatures, forming volatile tetrahalides, such as SiF4.
Unlike carbon, silicon does not readily form double or triple bonds. Silicon compounds of the general formula SiX4, where X is a highly electronegative group, can act as Lewis acids to form six-coordinate silicon. For example, silicon tetrafluoride, SiF4, reacts with sodium fluoride to yield Na2[SiF6], which contains the octahedral  ion in which silicon is sp3d2 hybridized:
Antimony reacts readily with stoichiometric amounts of fluorine, chlorine, bromine, or iodine, yielding trihalides or, with excess fluorine or chlorine, forming the pentahalides SbF5 and SbCl5. Depending on the stoichiometry, it forms antimony(III) sulfide, Sb2S3, or antimony(V) sulfide when heated with sulfur. As expected, the metallic nature of the element is greater than that of arsenic, which lies immediately above it in group 15.

### Boron and Silicon Halides

Boron trihalides—BF3, BCl3, BBr3, and BI3—can be prepared by the direct reaction of the elements. These nonpolar molecules contain boron with sp2 hybridization and a trigonal planar molecular geometry. The fluoride and chloride compounds are colorless gasses, the bromide is a liquid, and the iodide is a white crystalline solid.
Except for boron trifluoride, the boron trihalides readily hydrolyze in water to form boric acid and the corresponding hydrohalic acid. Boron trichloride reacts according to the equation:
Boron trifluoride reacts with hydrofluoric acid, to yield a solution of fluoroboric acid, HBF4:
In this reaction, the BF3 molecule acts as the Lewis acid (electron pair acceptor) and accepts a pair of electrons from a fluoride ion:
All the tetrahalides of silicon, SiX4, have been prepared. Silicon tetrachloride can be prepared by direct chlorination at elevated temperatures or by heating silicon dioxide with chlorine and carbon:
Silicon tetrachloride is a covalent tetrahedral molecule, which is a nonpolar, low-boiling (57 °C), colorless liquid.
It is possible to prepare silicon tetrafluoride by the reaction of silicon dioxide with hydrofluoric acid:
Hydrofluoric acid is the only common acid that will react with silicon dioxide or silicates. This reaction occurs because the silicon-fluorine bond is the only bond that silicon forms that is stronger than the silicon-oxygen bond. For this reason, it is possible to store all common acids, other than hydrofluoric acid, in glass containers.
Except for silicon tetrafluoride, silicon halides are extremely sensitive to water. Upon exposure to water, SiCl4 reacts rapidly with hydroxide groups, replacing all four chlorine atoms to produce unstable orthosilicic acid, Si(OH)4 or H4SiO4, which slowly decomposes into SiO2.

### Boron and Silicon Oxides and Derivatives

Boron burns at 700 °C in oxygen, forming boric oxide, B2O3. Boric oxide is necessary for the production of heat-resistant borosilicate glass, like that shown in  and certain optical glasses. Boric oxide dissolves in hot water to form boric acid, B(OH)3:
The boron atom in B(OH)3 is sp2 hybridized and is located at the center of an equilateral triangle with oxygen atoms at the corners. In solid B(OH)3, hydrogen bonding holds these triangular units together. Boric acid, shown in , is a very weak acid that does not act as a proton donor but rather as a Lewis acid, accepting an unshared pair of electrons from the Lewis base OH−:
Heating boric acid to 100 °C causes molecules of water to split out between pairs of adjacent –OH groups to form metaboric acid, HBO2. At about 150 °C, additional B-O-B linkages form, connecting the BO3 groups together with shared oxygen atoms to form tetraboric acid, H2B4O7. Complete water loss, at still higher temperatures, results in boric oxide.
Borates are salts of the oxyacids of boron. Borates result from the reactions of a base with an oxyacid or from the fusion of boric acid or boric oxide with a metal oxide or hydroxide. Borate anions range from the simple trigonal planar  ion to complex species containing chains and rings of three- and four-coordinated boron atoms. The structures of the anions found in CaB2O4, K[B5O6(OH)4]⋅2H2O (commonly written KB5O8⋅4H2O) and Na2[B4O5(OH)4]⋅8H2O (commonly written Na2B4O7⋅10H2O) are shown in . Commercially, the most important borate is borax, Na2[B4O5(OH)4]⋅8H2O, which is an important component of some laundry detergents. Most of the supply of borax comes directly from dry lakes, such as Searles Lake in California, or is prepared from kernite, Na2B4O7⋅4H2O.
Silicon dioxide, silica, occurs in both crystalline and amorphous forms. The usual crystalline form of silicon dioxide is quartz, a hard, brittle, clear, colorless solid. It is useful in many ways—for architectural decorations, semiprecious jewels, and frequency control in radio transmitters. Silica takes many crystalline forms, or polymorphs, in nature. Trace amounts of Fe3+ in quartz give amethyst its characteristic purple color. The term quartz is also used for articles such as tubing and lenses that are manufactured from amorphous silica. Opal is a naturally occurring form of amorphous silica.
The contrast in structure and physical properties between silicon dioxide and carbon dioxide is interesting, as illustrated in . Solid carbon dioxide (dry ice) contains single CO2 molecules with each of the two oxygen atoms attached to the carbon atom by double bonds. Very weak intermolecular forces hold the molecules together in the crystal. The volatility of dry ice reflect these weak forces between molecules. In contrast, silicon dioxide is a covalent network solid. In silicon dioxide, each silicon atom links to four oxygen atoms by single bonds directed toward the corners of a regular tetrahedron, and SiO4 tetrahedra share oxygen atoms. This arrangement gives a three dimensional, continuous, silicon-oxygen network. A quartz crystal is a macromolecule of silicon dioxide. The difference between these two compounds is the ability of the group 14 elements to form strong π bonds. Second-period elements, such as carbon, form very strong π bonds, which is why carbon dioxide forms small molecules with strong double bonds. Elements below the second period, such as silicon, do not form π bonds as readily as second-period elements, and when they do form, the π bonds are weaker than those formed by second-period elements. For this reason, silicon dioxide does not contain π bonds but only σ bonds.
At 1600 °C, quartz melts to yield a viscous liquid. When the liquid cools, it does not crystallize readily but usually supercools and forms a glass, also called silica. The SiO4 tetrahedra in glassy silica have a random arrangement characteristic of supercooled liquids, and the glass has some very useful properties. Silica is highly transparent to both visible and ultraviolet light. For this reason, it is important in the manufacture of lamps that give radiation rich in ultraviolet light and in certain optical instruments that operate with ultraviolet light. The coefficient of expansion of silica glass is very low; therefore, rapid temperature changes do not cause it to fracture. CorningWare and other ceramic cookware contain amorphous silica.
Silicates are salts containing anions composed of silicon and oxygen. In nearly all silicates, sp3-hybridized silicon atoms occur at the centers of tetrahedra with oxygen at the corners. There is a variation in the silicon-to-oxygen ratio that occurs because silicon-oxygen tetrahedra may exist as discrete, independent units or may share oxygen atoms at corners in a variety of ways. In addition, the presence of a variety of cations gives rise to the large number of silicate minerals.
Many ceramics are composed of silicates. By including small amounts of other compounds, it is possible to modify the physical properties of the silicate materials to produce ceramics with useful characteristics.

### Key Concepts and Summary

The elements boron, silicon, germanium, arsenic, antimony, and tellurium separate the metals from the nonmetals in the periodic table. These elements, called metalloids or sometimes semimetals, exhibit properties characteristic of both metals and nonmetals. The structures of these elements are similar in many ways to those of nonmetals, but the elements are electrical semiconductors.

### Chemistry End of Chapter Exercises


# Representative Metals, Metalloids, and Nonmetals

## Structure and General Properties of the Nonmetals

The nonmetals are elements located in the upper right portion of the periodic table. Their properties and behavior are quite different from those of metals on the left side. Under normal conditions, more than half of the nonmetals are gases, one is a liquid, and the rest include some of the softest and hardest of solids. The nonmetals exhibit a rich variety of chemical behaviors. They include the most reactive and least reactive of elements, and they form many different ionic and covalent compounds. This section presents an overview of the properties and chemical behaviors of the nonmetals, as well as the chemistry of specific elements. Many of these nonmetals are important in biological systems.
In many cases, trends in electronegativity enable us to predict the type of bonding and the physical states in compounds involving the nonmetals. We know that electronegativity decreases as we move down a given group and increases as we move from left to right across a period. The nonmetals have higher electronegativities than do metals, and compounds formed between metals and nonmetals are generally ionic in nature because of the large differences in electronegativity between them. The metals form cations, the nonmetals form anions, and the resulting compounds are solids under normal conditions. On the other hand, compounds formed between two or more nonmetals have small differences in electronegativity between the atoms, and covalent bonding—sharing of electrons—results. These substances tend to be molecular in nature and are gases, liquids, or volatile solids at room temperature and pressure.
In normal chemical processes, nonmetals do not form monatomic positive ions (cations) because their ionization energies are too high. All monatomic nonmetal ions are anions; examples include the chloride ion, Cl−, the nitride ion, N3−, and the selenide ion, Se2−.
The common oxidation states that the nonmetals exhibit in their ionic and covalent compounds are shown in . Remember that an element exhibits a positive oxidation state when combined with a more electronegative element and that it exhibits a negative oxidation state when combined with a less electronegative element.
The first member of each nonmetal group exhibits different behaviors, in many respects, from the other group members. The reasons for this include smaller size, greater ionization energy, and (most important) the fact that the first member of each group has only four valence orbitals (one 2s and three 2p) available for bonding, whereas other group members have empty d orbitals in their valence shells, making possible five, six, or even more bonds around the central atom. For example, nitrogen forms only NF3, whereas phosphorus forms both PF3 and PF5.
Another difference between the first group member and subsequent members is the greater ability of the first member to form π bonds. This is primarily a function of the smaller size of the first member of each group, which allows better overlap of atomic orbitals. Nonmetals, other than the first member of each group, rarely form π bonds to nonmetals that are the first member of a group. For example, sulfur-oxygen π bonds are well known, whereas sulfur does not normally form stable π bonds to itself.
The variety of oxidation states displayed by most of the nonmetals means that many of their chemical reactions involve changes in oxidation state through oxidation-reduction reactions. There are five general aspects of the oxidation-reduction chemistry:
1. Nonmetals oxidize most metals. The oxidation state of the metal becomes positive as it undergoes oxidation and that of the nonmetal becomes negative as it undergoes reduction. For example:

2. With the exception of nitrogen and carbon, which are poor oxidizing agents, a more electronegative nonmetal oxidizes a less electronegative nonmetal or the anion of the nonmetal:

3. Fluorine and oxygen are the strongest oxidizing agents within their respective groups; each oxidizes all the elements that lie below it in the group. Within any period, the strongest oxidizing agent is in group 17. A nonmetal often oxidizes an element that lies to its left in the same period. For example:

4. The stronger a nonmetal is as an oxidizing agent, the more difficult it is to oxidize the anion formed by the nonmetal. This means that the most stable negative ions are formed by elements at the top of the group or in group 17 of the period.
5. Fluorine and oxygen are the strongest oxidizing elements known. Fluorine does not form compounds in which it exhibits positive oxidation states; oxygen exhibits a positive oxidation state only when combined with fluorine. For example:

With the exception of most of the noble gases, all nonmetals form compounds with oxygen, yielding covalent oxides. Most of these oxides are acidic, that is, they react with water to form oxyacids. Recall from the acid-base chapter that an oxyacid is an acid consisting of hydrogen, oxygen, and some other element. Notable exceptions are carbon monoxide, CO, nitrous oxide, N2O, and nitric oxide, NO. There are three characteristics of these acidic oxides:
1. Oxides such as SO2 and N2O5, in which the nonmetal exhibits one of its common oxidation states, are acid anhydrides and react with water to form acids with no change in oxidation state. The product is an oxyacid. For example:

2. Those oxides such as NO2 and ClO2, in which the nonmetal does not exhibit one of its common oxidation states, also react with water. In these reactions, the nonmetal is both oxidized and reduced. For example:
Reactions in which the same element is both oxidized and reduced are called disproportionation reactions.
3. The acid strength increases as the electronegativity of the central atom increases. To learn more, see the discussion in the chapter on acid-base chemistry.
The binary hydrogen compounds of the nonmetals also exhibit an acidic behavior in water, although only HCl, HBr, and HI are strong acids. The acid strength of the nonmetal hydrogen compounds increases from left to right across a period and down a group. For example, ammonia, NH3, is a weaker acid than is water, H2O, which is weaker than is hydrogen fluoride, HF. Water, H2O, is also a weaker acid than is hydrogen sulfide, H2S, which is weaker than is hydrogen selenide, H2Se. Weaker acidic character implies greater basic character.

### Structures of the Nonmetals

The structures of the nonmetals differ dramatically from those of metals. Metals crystallize in closely packed arrays that do not contain molecules or covalent bonds. Nonmetal structures contain covalent bonds, and many nonmetals consist of individual molecules. The electrons in nonmetals are localized in covalent bonds, whereas in a metal, there is delocalization of the electrons throughout the solid.
The noble gases are all monatomic, whereas the other nonmetal gases—hydrogen, nitrogen, oxygen, fluorine, and chlorine—normally exist as the diatomic molecules H2, N2, O2, F2, and Cl2. The other halogens are also diatomic; Br2 is a liquid and I2 exists as a solid under normal conditions. The changes in state as one moves down the halogen family offer excellent examples of the increasing strength of intermolecular London forces with increasing molecular mass and increasing polarizability.
Oxygen has two allotropes: O2, dioxygen, and O3, ozone. Phosphorus has three common allotropes, commonly referred to by their colors: white, red, and black. Sulfur has several allotropes. There are also many carbon allotropes. Most people know of diamond, graphite, and charcoal, but fewer people know of the recent discovery of fullerenes, carbon nanotubes, and graphene.
Descriptions of the physical properties of three nonmetals that are characteristic of molecular solids follow.

### Carbon

Carbon occurs in the uncombined (elemental) state in many forms, such as diamond, graphite, charcoal, coke, carbon black, graphene, and fullerene.
Diamond, shown in , is a very hard crystalline material that is colorless and transparent when pure. Each atom forms four single bonds to four other atoms at the corners of a tetrahedron (sp3 hybridization); this makes the diamond a giant molecule. Carbon-carbon single bonds are very strong, and, because they extend throughout the crystal to form a three-dimensional network, the crystals are very hard and have high melting points (~4400 °C).
Graphite, also shown in , is a soft, slippery, grayish-black solid that conducts electricity. These properties relate to its structure, which consists of layers of carbon atoms, with each atom surrounded by three other carbon atoms in a trigonal planar arrangement. Each carbon atom in graphite forms three σ bonds, one to each of its nearest neighbors, by means of sp2-hybrid orbitals. The unhybridized p orbital on each carbon atom will overlap unhybridized orbitals on adjacent carbon atoms in the same layer to form π bonds. Many resonance forms are necessary to describe the electronic structure of a graphite layer;  illustrates two of these forms.
Atoms within a graphite layer are bonded together tightly by the σ and π bonds; however, the forces between layers are weak. London dispersion forces hold the layers together. To learn more, see the discussion of these weak forces in the chapter on liquids and solids. The weak forces between layers give graphite the soft, flaky character that makes it useful as the so-called “lead” in pencils and the slippery character that makes it useful as a lubricant. The loosely held electrons in the resonating π bonds can move throughout the solid and are responsible for the electrical conductivity of graphite.
Other forms of elemental carbon include carbon black, charcoal, and coke. Carbon black is an amorphous form of carbon prepared by the incomplete combustion of natural gas, CH4. It is possible to produce charcoal and coke by heating wood and coal, respectively, at high temperatures in the absence of air.
Recently, new forms of elemental carbon molecules have been identified in the soot generated by a smoky flame and in the vapor produced when graphite is heated to very high temperatures in a vacuum or in helium. One of these new forms, first isolated by Professor Richard Smalley and coworkers at Rice University, consists of icosahedral (soccer-ball-shaped) molecules that contain 60 carbon atoms, C60. This is buckminsterfullerene (often called bucky balls) after the architect Buckminster Fuller, who designed domed structures, which have a similar appearance ().

### Phosphorus

The name phosphorus comes from the Greek words meaning light bringing. When phosphorus was first isolated, scientists noted that it glowed in the dark and burned when exposed to air. Phosphorus is the only member of its group that does not occur in the uncombined state in nature; it exists in many allotropic forms. We will consider two of those forms: white phosphorus and red phosphorus.
White phosphorus is a white, waxy solid that melts at 44.2 °C and boils at 280 °C. It is insoluble in water (in which it is stored—see ), is very soluble in carbon disulfide, and bursts into flame in air. As a solid, as a liquid, as a gas, and in solution, white phosphorus exists as P4 molecules with four phosphorus atoms at the corners of a regular tetrahedron, as illustrated in . Each phosphorus atom covalently bonds to the other three atoms in the molecule by single covalent bonds. White phosphorus is the most reactive allotrope and is very toxic.
Heating white phosphorus to 270–300 °C in the absence of air yields red phosphorus. Red phosphorus (shown in ) is denser, has a higher melting point (~600 °C), is much less reactive, is essentially nontoxic, and is easier and safer to handle than is white phosphorus. Its structure is highly polymeric and appears to contain three-dimensional networks of P4 tetrahedra joined by P-P single bonds. Red phosphorus is insoluble in solvents that dissolve white phosphorus. When red phosphorus is heated, P4 molecules sublime from the solid.

### Sulfur

The allotropy of sulfur is far greater and more complex than that of any other element. Sulfur is the brimstone referred to in the Bible and other places, and references to sulfur occur throughout recorded history—right up to the relatively recent discovery that it is a component of the atmospheres of Venus and of Io, a moon of Jupiter. The most common and most stable allotrope of sulfur is yellow, rhombic sulfur, so named because of the shape of its crystals. Rhombic sulfur is the form to which all other allotropes revert at room temperature. Crystals of rhombic sulfur melt at 113 °C. Cooling this liquid gives long needles of monoclinic sulfur. This form is stable from 96 °C to the melting point, 119 °C. At room temperature, it gradually reverts to the rhombic form.
Both rhombic sulfur and monoclinic sulfur contain S8 molecules in which atoms form eight-membered, puckered rings that resemble crowns, as illustrated in . Each sulfur atom is bonded to each of its two neighbors in the ring by covalent S-S single bonds.
When rhombic sulfur melts, the straw-colored liquid is quite mobile; its viscosity is low because S8 molecules are essentially spherical and offer relatively little resistance as they move past each other. As the temperature rises, S-S bonds in the rings break, and polymeric chains of sulfur atoms result. These chains combine end to end, forming still longer chains that tangle with one another. The liquid gradually darkens in color and becomes so viscous that finally (at about 230 °C) it does not pour easily. The dangling atoms at the ends of the chains of sulfur atoms are responsible for the dark red color because their electronic structure differs from those of sulfur atoms that have bonds to two adjacent sulfur atoms. This causes them to absorb light differently and results in a different visible color. Cooling the liquid rapidly produces a rubberlike amorphous mass, called plastic sulfur.
Sulfur boils at 445 °C and forms a vapor consisting of S2, S6, and S8 molecules; at about 1000 °C, the vapor density corresponds to the formula S2, which is a paramagnetic molecule like O2 with a similar electronic structure and a weak sulfur-sulfur double bond.
As seen in this discussion, an important feature of the structural behavior of the nonmetals is that the elements usually occur with eight electrons in their valence shells. If necessary, the elements form enough covalent bonds to supplement the electrons already present to possess an octet. For example, members of group 15 have five valence electrons and require only three additional electrons to fill their valence shells. These elements form three covalent bonds in their free state: triple bonds in the N2 molecule or single bonds to three different atoms in arsenic and phosphorus. The elements of group 16 require only two additional electrons. Oxygen forms a double bond in the O2 molecule, and sulfur, selenium, and tellurium form two single bonds in various rings and chains. The halogens form diatomic molecules in which each atom is involved in only one bond. This provides the electron required necessary to complete the octet on the halogen atom. The noble gases do not form covalent bonds to other noble gas atoms because they already have a filled outer shell.

### Key Concepts and Summary

Nonmetals have structures that are very different from those of the metals, primarily because they have greater electronegativity and electrons that are more tightly bound to individual atoms. Most nonmetal oxides are acid anhydrides, meaning that they react with water to form acidic solutions. Molecular structures are common for most of the nonmetals, and several have multiple allotropes with varying physical properties.

### Chemistry End of Chapter Exercises


# Representative Metals, Metalloids, and Nonmetals

## Occurrence, Preparation, and Compounds of Hydrogen

Hydrogen is the most abundant element in the universe. The sun and other stars are composed largely of hydrogen. Astronomers estimate that 90% of the atoms in the universe are hydrogen atoms. Hydrogen is a component of more compounds than any other element. Water is the most abundant compound of hydrogen found on earth. Hydrogen is an important part of petroleum, many minerals, cellulose and starch, sugar, fats, oils, alcohols, acids, and thousands of other substances.
At ordinary temperatures, hydrogen is a colorless, odorless, tasteless, and nonpoisonous gas consisting of the diatomic molecule H2. Hydrogen is composed of three isotopes, and unlike other elements, these isotopes have different names and chemical symbols: protium, 1H, deuterium, 2H (or “D”), and tritium 3H (or “T”). In a naturally occurring sample of hydrogen, there is one atom of deuterium for every 7000 H atoms and one atom of radioactive tritium for every 1018 H atoms. The chemical properties of the different isotopes are very similar because they have identical electron structures, but they differ in some physical properties because of their differing atomic masses. Elemental deuterium and tritium have lower vapor pressure than ordinary hydrogen. Consequently, when liquid hydrogen evaporates, the heavier isotopes are concentrated in the last portions to evaporate. Electrolysis of heavy water, D2O, yields deuterium. Most tritium originates from nuclear reactions.

### Preparation of Hydrogen

Elemental hydrogen must be prepared from compounds by breaking chemical bonds. The most common methods of preparing hydrogen follow.

### From Steam and Carbon or Hydrocarbons

Water is the cheapest and most abundant source of hydrogen. Passing steam over coke (an impure form of elemental carbon) at 1000 °C produces a mixture of carbon monoxide and hydrogen known as water gas:
Water gas is as an industrial fuel. It is possible to produce additional hydrogen by mixing the water gas with steam in the presence of a catalyst to convert the CO to CO2. This reaction is the water gas shift reaction.
It is also possible to prepare a mixture of hydrogen and carbon monoxide by passing hydrocarbons from natural gas or petroleum and steam over a nickel-based catalyst. Propane is an example of a hydrocarbon reactant:

### Electrolysis

Hydrogen forms when direct current electricity passes through water containing an electrolyte such as H2SO4, as illustrated in . Bubbles of hydrogen form at the cathode, and oxygen evolves at the anode. The net reaction is:

### Reaction of Metals with Acids

This is the most convenient laboratory method of producing hydrogen. Metals with lower reduction potentials reduce the hydrogen ion in dilute acids to produce hydrogen gas and metal salts. For example, as shown in , iron in dilute hydrochloric acid produces hydrogen gas and iron(II) chloride:

### Reaction of Ionic Metal Hydrides with Water

It is possible to produce hydrogen from the reaction of hydrides of the active metals, which contain the very strongly basic H− anion, with water:
Metal hydrides are expensive but convenient sources of hydrogen, especially where space and weight are important factors. They are important in the inflation of life jackets, life rafts, and military balloons.

### Reactions

Under normal conditions, hydrogen is relatively inactive chemically, but when heated, it enters into many chemical reactions.
Two thirds of the world’s hydrogen production is devoted to the manufacture of ammonia, which is a fertilizer and used in the manufacture of nitric acid. Large quantities of hydrogen are also important in the process of hydrogenation, discussed in the chapter on organic chemistry.
It is possible to use hydrogen as a nonpolluting fuel. The reaction of hydrogen with oxygen is a very exothermic reaction, releasing 286 kJ of energy per mole of water formed. Hydrogen burns without explosion under controlled conditions. The oxygen-hydrogen torch, because of the high heat of combustion of hydrogen, can achieve temperatures up to 2800 °C. The hot flame of this torch is useful in cutting thick sheets of many metals. Liquid hydrogen is also an important rocket fuel ().
An uncombined hydrogen atom consists of a nucleus and one valence electron in the 1s orbital. The n = 1 valence shell has a capacity for two electrons, and hydrogen can rightfully occupy two locations in the periodic table. It is possible to consider hydrogen a group 1 element because hydrogen can lose an electron to form the cation, H+. It is also possible to consider hydrogen to be a group 17 element because it needs only one electron to fill its valence orbital to form a hydride ion, H−, or it can share an electron to form a single, covalent bond. In reality, hydrogen is a unique element that almost deserves its own location in the periodic table.

### Reactions with Elements

When heated, hydrogen reacts with the metals of group 1 and with Ca, Sr, and Ba (the more active metals in group 2). The compounds formed are crystalline, ionic hydrides that contain the hydride anion, H−, a strong reducing agent and a strong base, which reacts vigorously with water and other acids to form hydrogen gas.
The reactions of hydrogen with nonmetals generally produce acidic hydrogen compounds with hydrogen in the 1+ oxidation state. The reactions become more exothermic and vigorous as the electronegativity of the nonmetal increases. Hydrogen reacts with nitrogen and sulfur only when heated, but it reacts explosively with fluorine (forming HF) and, under some conditions, with chlorine (forming HCl). A mixture of hydrogen and oxygen explodes if ignited. Because of the explosive nature of the reaction, it is necessary to exercise caution when handling hydrogen (or any other combustible gas) to avoid the formation of an explosive mixture in a confined space. Although most hydrides of the nonmetals are acidic, ammonia and phosphine (PH3) are very, very weak acids and generally function as bases. There is a summary of these reactions of hydrogen with the elements in .

### Reaction with Compounds

Hydrogen reduces the heated oxides of many metals, with the formation of the metal and water vapor. For example, passing hydrogen over heated CuO forms copper and water.
Hydrogen may also reduce the metal ions in some metal oxides to lower oxidation states:

### Hydrogen Compounds

Other than the noble gases, each of the nonmetals forms compounds with hydrogen. For brevity, we will discuss only a few hydrogen compounds of the nonmetals here.

### Nitrogen Hydrogen Compounds

Ammonia, NH3, forms naturally when any nitrogen-containing organic material decomposes in the absence of air. The laboratory preparation of ammonia is by the reaction of an ammonium salt with a strong base such as sodium hydroxide. The acid-base reaction with the weakly acidic ammonium ion gives ammonia, illustrated in . Ammonia also forms when ionic nitrides react with water. The nitride ion is a much stronger base than the hydroxide ion:
The commercial production of ammonia is by the direct combination of the elements in the Haber process:
Ammonia is a colorless gas with a sharp, pungent odor. Smelling salts utilize this powerful odor. Gaseous ammonia readily liquefies to give a colorless liquid that boils at −33 °C. Due to intermolecular hydrogen bonding, the enthalpy of vaporization of liquid ammonia is higher than that of any other liquid except water, so ammonia is useful as a refrigerant. Ammonia is quite soluble in water (658 L at STP dissolves in 1 L H2O).
The chemical properties of ammonia are as follows:
1. Ammonia acts as a Brønsted base, as discussed in the chapter on acid-base chemistry. The ammonium ion is similar in size to the potassium ion; compounds of the two ions exhibit many similarities in their structures and solubilities.
2. Ammonia can display acidic behavior, although it is a much weaker acid than water. Like other acids, ammonia reacts with metals, although it is so weak that high temperatures are necessary. Hydrogen and (depending on the stoichiometry) amides (salts of  imides (salts of NH2−), or nitrides (salts of N3−) form.
3. The nitrogen atom in ammonia has its lowest possible oxidation state (3−) and thus is not susceptible to reduction. However, it can be oxidized. Ammonia burns in air, giving NO and water. Hot ammonia and the ammonium ion are active reducing agents. Of particular interest are the oxidations of ammonium ion by nitrite ion,  to yield pure nitrogen and by nitrate ion to yield nitrous oxide, N2O.
4. There are a number of compounds that we can consider derivatives of ammonia through the replacement of one or more hydrogen atoms with some other atom or group of atoms. Inorganic derivations include chloramine, NH2Cl, and hydrazine, N2H4:
Chloramine, NH2Cl, results from the reaction of sodium hypochlorite, NaOCl, with ammonia in basic solution. In the presence of a large excess of ammonia at low temperature, the chloramine reacts further to produce hydrazine, N2H4:
Anhydrous hydrazine is relatively stable in spite of its positive free energy of formation:
Hydrazine is a fuming, colorless liquid that has some physical properties remarkably similar to those of H2O (it melts at 2 °C, boils at 113.5 °C, and has a density at 25 °C of 1.00 g/mL). It burns rapidly and completely in air with substantial evolution of heat:
Like ammonia, hydrazine is both a Brønsted base and a Lewis base, although it is weaker than ammonia. It reacts with strong acids and forms two series of salts that contain the  and  ions, respectively. Some rockets use hydrazine as a fuel.

### Phosphorus Hydrogen Compounds

The most important hydride of phosphorus is phosphine, PH3, a gaseous analog of ammonia in terms of both formula and structure. Unlike ammonia, it is not possible to form phosphine by direct union of the elements. There are two methods for the preparation of phosphine. One method is by the action of an acid on an ionic phosphide. The other method is the disproportionation of white phosphorus with hot concentrated base to produce phosphine and the hydrogen phosphite ion:
Phosphine is a colorless, very poisonous gas, which has an odor like that of decaying fish. Heat easily decomposes phosphine  and the compound burns in air. The major uses of phosphine are as a fumigant for grains and in semiconductor processing. Like ammonia, gaseous phosphine unites with gaseous hydrogen halides, forming phosphonium compounds like PH4Cl and PH4I. Phosphine is a much weaker base than ammonia; therefore, these compounds decompose in water, and the insoluble PH3 escapes from solution.

### Sulfur Hydrogen Compounds

Hydrogen sulfide, H2S, is a colorless gas that is responsible for the offensive odor of rotten eggs and of many hot springs. Hydrogen sulfide is as toxic as hydrogen cyanide; therefore, it is necessary to exercise great care in handling it. Hydrogen sulfide is particularly deceptive because it paralyzes the olfactory nerves; after a short exposure, one does not smell it.
The production of hydrogen sulfide by the direct reaction of the elements (H2 + S) is unsatisfactory because the yield is low. A more effective preparation method is the reaction of a metal sulfide with a dilute acid. For example:
It is easy to oxidize the sulfur in metal sulfides and in hydrogen sulfide, making metal sulfides and H2S good reducing agents. In acidic solutions, hydrogen sulfide reduces Fe3+ to Fe2+,  to Mn2+,  to Cr3+, and HNO3 to NO2. The sulfur in H2S usually oxidizes to elemental sulfur, unless a large excess of the oxidizing agent is present. In which case, the sulfide may oxidize to  or  (or to SO2 or SO3 in the absence of water):
This oxidation process leads to the removal of the hydrogen sulfide found in many sources of natural gas. The deposits of sulfur in volcanic regions may be the result of the oxidation of H2S present in volcanic gases.
Hydrogen sulfide is a weak diprotic acid that dissolves in water to form hydrosulfuric acid. The acid ionizes in two stages, yielding hydrogen sulfide ions, HS−, in the first stage and sulfide ions, S2−, in the second. Since hydrogen sulfide is a weak acid, aqueous solutions of soluble sulfides and hydrogen sulfides are basic:

### Halogen Hydrogen Compounds

Binary compounds containing only hydrogen and a halogen are hydrogen halides. At room temperature, the pure hydrogen halides HF, HCl, HBr, and HI are gases.
In general, it is possible to prepare the halides by the general techniques used to prepare other acids. Fluorine, chlorine, and bromine react directly with hydrogen to form the respective hydrogen halide. This is a commercially important reaction for preparing hydrogen chloride and hydrogen bromide.
The acid-base reaction between a nonvolatile strong acid and a metal halide will yield a hydrogen halide. The escape of the gaseous hydrogen halide drives the reaction to completion. For example, the usual method of preparing hydrogen fluoride is by heating a mixture of calcium fluoride, CaF2, and concentrated sulfuric acid:
Gaseous hydrogen fluoride is also a by-product in the preparation of phosphate fertilizers by the reaction of fluoroapatite, Ca5(PO4)3F, with sulfuric acid. The reaction of concentrated sulfuric acid with a chloride salt produces hydrogen chloride both commercially and in the laboratory.
In most cases, sodium chloride is the chloride of choice because it is the least expensive chloride. Hydrogen bromide and hydrogen iodide cannot be prepared using sulfuric acid because this acid is an oxidizing agent capable of oxidizing both bromide and iodide. However, it is possible to prepare both hydrogen bromide and hydrogen iodide using an acid such as phosphoric acid because it is a weaker oxidizing agent. For example:
All of the hydrogen halides are very soluble in water, forming hydrohalic acids. With the exception of hydrogen fluoride, which has a strong hydrogen-fluoride bond, they are strong acids. Reactions of hydrohalic acids with metals, metal hydroxides, oxides, or carbonates produce salts of the halides. Most chloride salts are soluble in water. AgCl, PbCl2, and Hg2Cl2 are the commonly encountered exceptions.
The halide ions give the substances the properties associated with X−(aq). The heavier halide ions (Cl−, Br−, and I−) can act as reducing agents, and the lighter halogens or other oxidizing agents will oxidize them:
For example, bromine oxidizes iodine:
Hydrofluoric acid is unique in its reactions with sand (silicon dioxide) and with glass, which is a mixture of silicates:
The volatile silicon tetrafluoride escapes from these reactions. Because hydrogen fluoride attacks glass, it can frost or etch glass and is used to etch markings on thermometers, burets, and other glassware.
The largest use for hydrogen fluoride is in production of hydrochlorofluorocarbons for refrigerants, in plastics, and in propellants. The second largest use is in the manufacture of cryolite, Na3AlF6, which is important in the production of aluminum. The acid is also important in the production of other inorganic fluorides (such as BF3), which serve as catalysts in the industrial synthesis of certain organic compounds.
Hydrochloric acid is relatively inexpensive. It is an important and versatile acid in industry and is important for the manufacture of metal chlorides, dyes, glue, glucose, and various other chemicals. A considerable amount is also important for the activation of oil wells and as pickle liquor—an acid used to remove oxide coating from iron or steel that is to be galvanized, tinned, or enameled. The amounts of hydrobromic acid and hydroiodic acid used commercially are insignificant by comparison.

### Key Concepts and Summary

Hydrogen is the most abundant element in the universe and its chemistry is truly unique. Although it has some chemical reactivity that is similar to that of the alkali metals, hydrogen has many of the same chemical properties of a nonmetal with a relatively low electronegativity. It forms ionic hydrides with active metals, covalent compounds in which it has an oxidation state of 1− with less electronegative elements, and covalent compounds in which it has an oxidation state of 1+ with more electronegative nonmetals. It reacts explosively with oxygen, fluorine, and chlorine, less readily with bromine, and much less readily with iodine, sulfur, and nitrogen. Hydrogen reduces the oxides of metals with lower reduction potentials than chromium to form the metal and water. The hydrogen halides are all acidic when dissolved in water.

### Chemistry End of Chapter Exercises


# Representative Metals, Metalloids, and Nonmetals

## Occurrence, Preparation, and Properties of Carbonates

The chemistry of carbon is extensive; however, most of this chemistry is not relevant to this chapter. The other aspects of the chemistry of carbon will appear in the chapter covering organic chemistry. In this chapter, we will focus on the carbonate ion and related substances. The metals of groups 1 and 2, as well as zinc, cadmium, mercury, and lead(II), form ionic carbonates—compounds that contain the carbonate anions,  The metals of group 1, magnesium, calcium, strontium, and barium also form hydrogen carbonates—compounds that contain the hydrogen carbonate anion,  also known as the bicarbonate anion.
With the exception of magnesium carbonate, it is possible to prepare carbonates of the metals of groups 1 and 2 by the reaction of carbon dioxide with the respective oxide or hydroxide. Examples of such reactions include:
The carbonates of the alkaline earth metals of group 12 and lead(II) are not soluble. These carbonates precipitate upon mixing a solution of soluble alkali metal carbonate with a solution of soluble salts of these metals. Examples of net ionic equations for the reactions are:
Pearls and the shells of most mollusks are calcium carbonate. Tin(II) or one of the trivalent or tetravalent ions such as Al3+ or Sn4+ behave differently in this reaction as carbon dioxide and the corresponding oxide form instead of the carbonate.
Alkali metal hydrogen carbonates such as NaHCO3 and CsHCO3 form by saturating a solution of the hydroxides with carbon dioxide. The net ionic reaction involves hydroxide ion and carbon dioxide:
It is possible to isolate the solids by evaporation of the water from the solution.
Although they are insoluble in pure water, alkaline earth carbonates dissolve readily in water containing carbon dioxide because hydrogen carbonate salts form. For example, caves and sinkholes form in limestone when CaCO3 dissolves in water containing dissolved carbon dioxide:
Hydrogen carbonates of the alkaline earth metals remain stable only in solution; evaporation of the solution produces the carbonate. Stalactites and stalagmites, like those shown in , form in caves when drops of water containing dissolved calcium hydrogen carbonate evaporate to leave a deposit of calcium carbonate.
The two carbonates used commercially in the largest quantities are sodium carbonate and calcium carbonate. In the United States, sodium carbonate is extracted from the mineral trona, Na3(CO3)(HCO3)(H2O)2. Following recrystallization to remove clay and other impurities, heating the recrystallized trona produces Na2CO3:
Carbonates are moderately strong bases. Aqueous solutions are basic because the carbonate ion accepts hydrogen ion from water in this reversible reaction:
Carbonates react with acids to form salts of the metal, gaseous carbon dioxide, and water. The reaction of calcium carbonate, the active ingredient of the antacid Tums, with hydrochloric acid (stomach acid), as shown in , illustrates the reaction:
Other applications of carbonates include glass making—where carbonate ions serve as a source of oxide ions—and synthesis of oxides.
Hydrogen carbonates are amphoteric because they act as both weak acids and weak bases. Hydrogen carbonate ions act as acids and react with solutions of soluble hydroxides to form a carbonate and water:
With acids, hydrogen carbonates form a salt, carbon dioxide, and water. Baking soda (bicarbonate of soda or sodium bicarbonate) is sodium hydrogen carbonate. Baking powder contains baking soda and a solid acid such as potassium hydrogen tartrate (cream of tartar), KHC4H4O6. As long as the powder is dry, no reaction occurs; immediately after the addition of water, the acid reacts with the hydrogen carbonate ions to form carbon dioxide:
Dough will trap the carbon dioxide, causing it to expand during baking, producing the characteristic texture of baked goods.

### Key Concepts and Summary

The usual method for the preparation of the carbonates of the alkali and alkaline earth metals is by reaction of an oxide or hydroxide with carbon dioxide. Other carbonates form by precipitation. Metal carbonates or hydrogen carbonates such as limestone (CaCO3), the antacid Tums (CaCO3), and baking soda (NaHCO3) are common examples. Carbonates and hydrogen carbonates decompose in the presence of acids and most decompose on heating.

### Chemistry End of Chapter Exercises


# Representative Metals, Metalloids, and Nonmetals

## Occurrence, Preparation, and Properties of Nitrogen

Most pure nitrogen comes from the fractional distillation of liquid air. The atmosphere consists of 78% nitrogen by volume. This means there are more than 20 million tons of nitrogen over every square mile of the earth’s surface. Nitrogen is a component of proteins and of the genetic material (DNA/RNA) of all plants and animals.
Under ordinary conditions, nitrogen is a colorless, odorless, and tasteless gas. It boils at 77 K and freezes at 63 K. Liquid nitrogen is a useful coolant because it is inexpensive and has a low boiling point. Nitrogen is very unreactive because of the very strong triple bond between the nitrogen atoms. The only common reactions at room temperature occur with lithium to form Li3N, with certain transition metal complexes, and with hydrogen or oxygen in nitrogen-fixing bacteria. The general lack of reactivity of nitrogen makes the remarkable ability of some bacteria to synthesize nitrogen compounds using atmospheric nitrogen gas as the source one of the most exciting chemical events on our planet. This process is one type of nitrogen fixation. In this case, nitrogen fixation is the process where organisms convert atmospheric nitrogen into biologically useful chemicals. Nitrogen fixation also occurs when lightning passes through air, causing molecular nitrogen to react with oxygen to form nitrogen oxides, which are then carried down to the soil.
Large volumes of atmospheric nitrogen are necessary for making ammonia—the principal starting material used for preparation of large quantities of other nitrogen-containing compounds. Most other uses for elemental nitrogen depend on its inactivity. It is helpful when a chemical process requires an inert atmosphere. Canned foods and luncheon meats cannot oxidize in a pure nitrogen atmosphere, so they retain a better flavor and color, and spoil less rapidly, when sealed in nitrogen instead of air. This technology allows fresh produce to be available year-round, regardless of growing season.
There are compounds with nitrogen in all of its oxidation states from 3− to 5+. Much of the chemistry of nitrogen involves oxidation-reduction reactions. Some active metals (such as alkali metals and alkaline earth metals) can reduce nitrogen to form metal nitrides. In the remainder of this section, we will examine nitrogen-oxygen chemistry.
There are well-characterized nitrogen oxides in which nitrogen exhibits each of its positive oxidation numbers from 1+ to 5+. When ammonium nitrate is carefully heated, nitrous oxide (dinitrogen oxide) and water vapor form. Stronger heating generates nitrogen gas, oxygen gas, and water vapor. No one should ever attempt this reaction—it can be very explosive. In 1947, there was a major ammonium nitrate explosion in Texas City, Texas, and, in 2013, there was another major explosion in West, Texas. In the last 100 years, there were nearly 30 similar disasters worldwide, resulting in the loss of numerous lives. In this oxidation-reduction reaction, the nitrogen in the nitrate ion oxidizes the nitrogen in the ammonium ion. Nitrous oxide, shown in , is a colorless gas possessing a mild, pleasing odor and a sweet taste. It finds application as an anesthetic for minor operations, especially in dentistry, under the name “laughing gas.”
Low yields of nitric oxide, NO, form when heating nitrogen and oxygen together. NO also forms when lightning passes through air during thunderstorms. Burning ammonia is the commercial method of preparing nitric oxide. In the laboratory, the reduction of nitric acid is the best method for preparing nitric oxide. When copper reacts with dilute nitric acid, nitric oxide is the principal reduction product:
Gaseous nitric oxide is the most thermally stable of the nitrogen oxides and is the simplest known thermally stable molecule with an unpaired electron. It is one of the air pollutants generated by internal combustion engines, resulting from the reaction of atmospheric nitrogen and oxygen during the combustion process.
At room temperature, nitric oxide is a colorless gas consisting of diatomic molecules. As is often the case with molecules that contain an unpaired electron, two molecules combine to form a dimer by pairing their unpaired electrons to form a bond. Liquid and solid NO both contain N2O2 dimers, like that shown in . Most substances with unpaired electrons exhibit color by absorbing visible light; however, NO is colorless because the absorption of light is not in the visible region of the spectrum.
Cooling a mixture of equal parts nitric oxide and nitrogen dioxide to −21 °C produces dinitrogen trioxide, a blue liquid consisting of N2O3 molecules (shown in ). Dinitrogen trioxide exists only in the liquid and solid states. When heated, it reverts to a mixture of NO and NO2.
It is possible to prepare nitrogen dioxide in the laboratory by heating the nitrate of a heavy metal, or by the reduction of concentrated nitric acid with copper metal, as shown in . Commercially, it is possible to prepare nitrogen dioxide by oxidizing nitric oxide with air.
The nitrogen dioxide molecule (illustrated in ) contains an unpaired electron, which is responsible for its color and paramagnetism. It is also responsible for the dimerization of NO2. At low pressures or at high temperatures, nitrogen dioxide has a deep brown color that is due to the presence of the NO2 molecule. At low temperatures, the color almost entirely disappears as dinitrogen tetraoxide, N2O4, forms. At room temperature, an equilibrium exists:
Dinitrogen pentaoxide, N2O5 (illustrated in ), is a white solid that is formed by the dehydration of nitric acid by phosphorus(V) oxide (tetraphosphorus decoxide):
It is unstable above room temperature, decomposing to N2O4 and O2.
The oxides of nitrogen(III), nitrogen(IV), and nitrogen(V) react with water and form nitrogen-containing oxyacids. Nitrogen(III) oxide, N2O3, is the anhydride of nitrous acid; HNO2 forms when N2O3 reacts with water. There are no stable oxyacids containing nitrogen with an oxidation state of 4+; therefore, nitrogen(IV) oxide, NO2, disproportionates in one of two ways when it reacts with water. In cold water, a mixture of HNO2 and HNO3 forms. At higher temperatures, HNO3 and NO will form. Nitrogen(V) oxide, N2O5, is the anhydride of nitric acid; HNO3 is produced when N2O5 reacts with water:
The nitrogen oxides exhibit extensive oxidation-reduction behavior. Nitrous oxide resembles oxygen in its behavior when heated with combustible substances. N2O is a strong oxidizing agent that decomposes when heated to form nitrogen and oxygen. Because one-third of the gas liberated is oxygen, nitrous oxide supports combustion better than air (one-fifth oxygen). A glowing splinter bursts into flame when thrust into a bottle of this gas. Nitric oxide acts both as an oxidizing agent and as a reducing agent. For example:
Nitrogen dioxide (or dinitrogen tetraoxide) is a good oxidizing agent. For example:

### Key Concepts and Summary

Nitrogen exhibits oxidation states ranging from 3− to 5+. Because of the stability of the N≡N triple bond, it requires a great deal of energy to make compounds from molecular nitrogen. Active metals such as the alkali metals and alkaline earth metals can reduce nitrogen to form metal nitrides. Nitrogen oxides and nitrogen hydrides are also important substances.

### Chemistry End of Chapter Exercises


# Representative Metals, Metalloids, and Nonmetals

## Occurrence, Preparation, and Properties of Phosphorus

The industrial preparation of phosphorus is by heating calcium phosphate, obtained from phosphate rock, with sand and coke:
The phosphorus distills out of the furnace and is condensed into a solid or burned to form P4O10. The preparation of many other phosphorus compounds begins with P4O10. The acids and phosphates are useful as fertilizers and in the chemical industry. Other uses are in the manufacture of special alloys such as ferrophosphorus and phosphor bronze. Phosphorus is important in making pesticides, matches, and some plastics. Phosphorus is an active nonmetal. In compounds, phosphorus usually occurs in oxidation states of 3−, 3+, and 5+. Phosphorus exhibits oxidation numbers that are unusual for a group 15 element in compounds that contain phosphorus-phosphorus bonds; examples include diphosphorus tetrahydride, H2P-PH2, and tetraphosphorus trisulfide, P4S3, illustrated in .

### Phosphorus Oxygen Compounds

Phosphorus forms two common oxides, phosphorus(III) oxide (or tetraphosphorus hexaoxide), P4O6, and phosphorus(V) oxide (or tetraphosphorus decaoxide), P4O10, both shown in . Phosphorus(III) oxide is a white crystalline solid with a garlic-like odor. Its vapor is very poisonous. It oxidizes slowly in air and inflames when heated to 70 °C, forming P4O10. Phosphorus(III) oxide dissolves slowly in cold water to form phosphorous acid, H3PO3.
Phosphorus(V) oxide, P4O10, is a white powder that is prepared by burning phosphorus in excess oxygen. Its enthalpy of formation is very high (−2984 kJ), and it is quite stable and a very poor oxidizing agent. Dropping P4O10 into water produces a hissing sound, heat, and orthophosphoric acid:
Because of its great affinity for water, phosphorus(V) oxide is an excellent drying agent for gases and solvents, and for removing water from many compounds.

### Phosphorus Halogen Compounds

Phosphorus will react directly with the halogens, forming trihalides, PX3, and pentahalides, PX5. The trihalides are much more stable than the corresponding nitrogen trihalides; nitrogen pentahalides do not form because of nitrogen’s inability to form more than four bonds.
The chlorides PCl3 and PCl5, both shown in , are the most important halides of phosphorus. Phosphorus trichloride is a colorless liquid that is prepared by passing chlorine over molten phosphorus. Phosphorus pentachloride is an off-white solid that is prepared by oxidizing the trichloride with excess chlorine. The pentachloride sublimes when warmed and forms an equilibrium with the trichloride and chlorine when heated.
Like most other nonmetal halides, both phosphorus chlorides react with an excess of water and yield hydrogen chloride and an oxyacid: PCl3 yields phosphorous acid H3PO3 and PCl5 yields phosphoric acid, H3PO4.
The pentahalides of phosphorus are Lewis acids because of the empty valence d orbitals of phosphorus. These compounds readily react with halide ions (Lewis bases) to give the anion  Whereas phosphorus pentafluoride is a molecular compound in all states, X-ray studies show that solid phosphorus pentachloride is an ionic compound,  as are phosphorus pentabromide, [Br−], and phosphorus pentaiodide, [I−].

### Key Concepts and Summary

Phosphorus (group 15) commonly exhibits oxidation states of 3− with active metals and of 3+ and 5+ with more electronegative nonmetals. The halogens and oxygen will oxidize phosphorus. The oxides are phosphorus(V) oxide, P4O10, and phosphorus(III) oxide, P4O6. The two common methods for preparing orthophosphoric acid, H3PO4, are either the reaction of a phosphate with sulfuric acid or the reaction of water with phosphorus(V) oxide. Orthophosphoric acid is a triprotic acid that forms three types of salts.

### Chemistry End of Chapter Exercises


# Representative Metals, Metalloids, and Nonmetals

## Occurrence, Preparation, and Compounds of Oxygen

Oxygen is the most abundant element on the earth’s crust. The earth’s surface is composed of the crust, atmosphere, and hydrosphere. About 50% of the mass of the earth’s crust consists of oxygen (combined with other elements, principally silicon). Oxygen occurs as O2 molecules and, to a limited extent, as O3 (ozone) molecules in air. It forms about 20% of the mass of the air. About 89% of water by mass consists of combined oxygen. In combination with carbon, hydrogen, and nitrogen, oxygen is a large part of plants and animals.
Oxygen is a colorless, odorless, and tasteless gas at ordinary temperatures. It is slightly denser than air. Although it is only slightly soluble in water (49 mL of gas dissolves in 1 L at STP), oxygen’s solubility is very important to aquatic life.
Most of the oxygen isolated commercially comes from air and the remainder from the electrolysis of water. The separation of oxygen from air begins with cooling and compressing the air until it liquefies. As liquid air warms, oxygen with its higher boiling point (90 K) separates from nitrogen, which has a lower boiling point (77 K). It is possible to separate the other components of air at the same time based on differences in their boiling points.
Oxygen is essential in combustion processes such as the burning of fuels. Plants and animals use the oxygen from the air in respiration. The administration of oxygen-enriched air is an important medical practice when a patient is receiving an inadequate supply of oxygen because of shock, pneumonia, or some other illness.
The chemical industry employs oxygen for oxidizing many substances. A significant amount of oxygen produced commercially is important in the removal of carbon from iron during steel production. Large quantities of pure oxygen are also necessary in metal fabrication and in the cutting and welding of metals with oxyhydrogen and oxyacetylene torches.
Liquid oxygen is important to the space industry. It is an oxidizing agent in rocket engines. It is also the source of gaseous oxygen for life support in space.
As we know, oxygen is very important to life. The energy required for the maintenance of normal body functions in human beings and in other organisms comes from the slow oxidation of chemical compounds. Oxygen is the final oxidizing agent in these reactions. In humans, oxygen passes from the lungs into the blood, where it combines with hemoglobin, producing oxyhemoglobin. In this form, blood transports the oxygen to tissues, where it is transferred to the tissues. The ultimate products are carbon dioxide and water. The blood carries the carbon dioxide through the veins to the lungs, where the blood releases the carbon dioxide and collects another supply of oxygen. Digestion and assimilation of food regenerate the materials consumed by oxidation in the body; the energy liberated is the same as if the food burned outside the body.
Green plants continually replenish the oxygen in the atmosphere by a process called photosynthesis. The products of photosynthesis may vary, but, in general, the process converts carbon dioxide and water into glucose (a sugar) and oxygen using the energy of light:
Thus, the oxygen that became carbon dioxide and water by the metabolic processes in plants and animals returns to the atmosphere by photosynthesis.
When dry oxygen is passed between two electrically charged plates, ozone (O3, illustrated in ), an allotrope of oxygen possessing a distinctive odor, forms. The formation of ozone from oxygen is an endothermic reaction, in which the energy comes from an electrical discharge, heat, or ultraviolet light:
The sharp odor associated with sparking electrical equipment is due, in part, to ozone.
Ozone forms naturally in the upper atmosphere by the action of ultraviolet light from the sun on the oxygen there. Most atmospheric ozone occurs in the stratosphere, a layer of the atmosphere extending from about 10 to 50 kilometers above the earth’s surface. This ozone acts as a barrier to harmful ultraviolet light from the sun by absorbing it via a chemical decomposition reaction:
The reactive oxygen atoms recombine with molecular oxygen to complete the ozone cycle. The presence of stratospheric ozone decreases the frequency of skin cancer and other damaging effects of ultraviolet radiation. It has been clearly demonstrated that chlorofluorocarbons, CFCs (known commercially as Freons), which were present as aerosol propellants in spray cans and as refrigerants, caused depletion of ozone in the stratosphere. This occurred because ultraviolet light also causes CFCs to decompose, producing atomic chlorine. The chlorine atoms react with ozone molecules, resulting in a net removal of O3 molecules from stratosphere. This process is explored in detail in our coverage of chemical kinetics. There is a worldwide effort to reduce the amount of CFCs used commercially, and the ozone hole is already beginning to decrease in size as atmospheric concentrations of atomic chlorine decrease. While ozone in the stratosphere helps protect us, ozone in the troposphere is a problem. This ozone is a toxic component of photochemical smog.
The uses of ozone depend on its reactivity with other substances. It can be used as a bleaching agent for oils, waxes, fabrics, and starch: It oxidizes the colored compounds in these substances to colorless compounds. It is an alternative to chlorine as a disinfectant for water.

### Reactions

Elemental oxygen is a strong oxidizing agent. It reacts with most other elements and many compounds.

### Reaction with Elements

Oxygen reacts directly at room temperature or at elevated temperatures with all other elements except the noble gases, the halogens, and few second- and third-row transition metals of low reactivity (those with higher reduction potentials than copper). Rust is an example of the reaction of oxygen with iron. The more active metals form peroxides or superoxides. Less active metals and the nonmetals give oxides. Two examples of these reactions are:
The oxides of halogens, at least one of the noble gases, and metals with higher reduction potentials than copper do not form by the direct action of the elements with oxygen.

### Reaction with Compounds

Elemental oxygen also reacts with some compounds. If it is possible to oxidize any of the elements in a given compound, further oxidation by oxygen can occur. For example, hydrogen sulfide, H2S, contains sulfur with an oxidation state of 2−. Because the sulfur does not exhibit its maximum oxidation state, we would expect H2S to react with oxygen. It does, yielding water and sulfur dioxide. The reaction is:
It is also possible to oxidize oxides such as CO and P4O6 that contain an element with a lower oxidation state. The ease with which elemental oxygen picks up electrons is mirrored by the difficulty of removing electrons from oxygen in most oxides. Of the elements, only the very reactive fluorine can oxidize oxides to form oxygen gas.

### Oxides, Peroxides, and Hydroxides

Compounds of the representative metals with oxygen fall into three categories: (1) oxides, containing oxide ions, O2−; (2) peroxides, containing peroxides ions,  with oxygen-oxygen covalent single bonds and a very limited number of superoxides, containing superoxide ions,  with oxygen-oxygen covalent bonds that have a bond order of  In addition, there are (3) hydroxides, containing hydroxide ions, OH−. All representative metals form oxides. Some of the metals of group 2 also form peroxides, MO2, and the metals of group 1 also form peroxides, M2O2, and superoxides, MO2.

### Oxides

It is possible to produce the oxides of most representative metals by heating the corresponding hydroxides (forming the oxide and gaseous water) or carbonates (forming the oxide and gaseous CO2). Equations for example reactions are:
However, alkali metal salts generally are very stable and do not decompose easily when heated. Alkali metal oxides result from the oxidation-reduction reactions created by heating nitrates or hydroxides with the metals. Equations for sample reactions are:
With the exception of mercury(II) oxide, it is possible to produce the oxides of the metals of groups 2–15 by burning the corresponding metal in air. The heaviest member of each group, the member for which the inert pair effect is most pronounced, forms an oxide in which the oxidation state of the metal ion is two less than the group oxidation state (inert pair effect). Thus, Tl2O, PbO, and Bi2O3 form when burning thallium, lead, and bismuth, respectively. The oxides of the lighter members of each group exhibit the group oxidation state. For example, SnO2 forms from burning tin. Mercury(II) oxide, HgO, forms slowly when mercury is warmed below 500 °C; it decomposes at higher temperatures.
Burning the members of groups 1 and 2 in air is not a suitable way to form the oxides of these elements. These metals are reactive enough to combine with nitrogen in the air, so they form mixtures of oxides and ionic nitrides. Several also form peroxides or superoxides when heated in air.
Ionic oxides all contain the oxide ion, a very powerful hydrogen ion acceptor. With the exception of the very insoluble aluminum oxide, Al2O3, tin(IV), SnO2, and lead(IV), PbO2, the oxides of the representative metals react with acids to form salts. Some equations for these reactions are:
The oxides of the metals of groups 1 and 2 and of thallium(I) oxide react with water and form hydroxides. Examples of such reactions are:
The oxides of the alkali metals have little industrial utility, unlike magnesium oxide, calcium oxide, and aluminum oxide. Magnesium oxide is important in making firebrick, crucibles, furnace linings, and thermal insulation—applications that require chemical and thermal stability. Calcium oxide, sometimes called quicklime or lime in the industrial market, is very reactive, and its principal uses reflect its reactivity. Pure calcium oxide emits an intense white light when heated to a high temperature (as illustrated in ). Blocks of calcium oxide heated by gas flames were the stage lights in theaters before electricity was available. This is the source of the phrase “in the limelight.”
Calcium oxide and calcium hydroxide are inexpensive bases used extensively in chemical processing, although most of the useful products prepared from them do not contain calcium. Calcium oxide, CaO, is made by heating calcium carbonate, CaCO3, which is widely and inexpensively available as limestone or oyster shells:
Although this decomposition reaction is reversible, it is possible to obtain a 100% yield of CaO by allowing the CO2 to escape. It is possible to prepare calcium hydroxide by the familiar acid-base reaction of a soluble metal oxide with water:
Both CaO and Ca(OH)2 are useful as bases; they accept protons and neutralize acids.
Alumina (Al2O3) occurs in nature as the mineral corundum, a very hard substance used as an abrasive for grinding and polishing. Corundum is important to the jewelry trade as ruby and sapphire. The color of ruby is due to the presence of a small amount of chromium; other impurities produce the wide variety of colors possible for sapphires. Artificial rubies and sapphires are now manufactured by melting aluminum oxide (melting point = 2050 °C) with small amounts of oxides to produce the desired colors and cooling the melt in such a way as to produce large crystals. Ruby lasers use synthetic ruby crystals.
Zinc oxide, ZnO, was a useful white paint pigment; however, pollutants tend to discolor the compound. The compound is also important in the manufacture of automobile tires and other rubber goods, and in the preparation of medicinal ointments. For example, zinc-oxide-based sunscreens, as shown in , help prevent sunburn. The zinc oxide in these sunscreens is present in the form of very small grains known as nanoparticles. Lead dioxide is a constituent of charged lead storage batteries. Lead(IV) tends to revert to the more stable lead(II) ion by gaining two electrons, so lead dioxide is a powerful oxidizing agent.

### Peroxides and Superoxides

Peroxides and superoxides are strong oxidizers and are important in chemical processes. Hydrogen peroxide, H2O2, prepared from metal peroxides, is an important bleach and disinfectant. Peroxides and superoxides form when the metal or metal oxides of groups 1 and 2 react with pure oxygen at elevated temperatures. Sodium peroxide and the peroxides of calcium, strontium, and barium form by heating the corresponding metal or metal oxide in pure oxygen:
The peroxides of potassium, rubidium, and cesium can be prepared by heating the metal or its oxide in a carefully controlled amount of oxygen:
With an excess of oxygen, the superoxides KO2, RbO2, and CsO2 form. For example:
The stability of the peroxides and superoxides of the alkali metals increases as the size of the cation increases.

### Hydroxides

Hydroxides are compounds that contain the OH− ion. It is possible to prepare these compounds by two general types of reactions. Soluble metal hydroxides can be produced by the reaction of the metal or metal oxide with water. Insoluble metal hydroxides form when a solution of a soluble salt of the metal combines with a solution containing hydroxide ions.
With the exception of beryllium and magnesium, the metals of groups 1 and 2 react with water to form hydroxides and hydrogen gas. Examples of such reactions include:
However, these reactions can be violent and dangerous; therefore, it is preferable to produce soluble metal hydroxides by the reaction of the respective oxide with water:
Most metal oxides are base anhydrides. This is obvious for the soluble oxides because they form metal hydroxides. Most other metal oxides are insoluble and do not form hydroxides in water; however, they are still base anhydrides because they will react with acids.
It is possible to prepare the insoluble hydroxides of beryllium, magnesium, and other representative metals by the addition of sodium hydroxide to a solution of a salt of the respective metal. The net ionic equations for the reactions involving a magnesium salt, an aluminum salt, and a zinc salt are:
An excess of hydroxide must be avoided when preparing aluminum, gallium, zinc, and tin(II) hydroxides, or the hydroxides will dissolve with the formation of the corresponding complex ions:    and  (see ). The important aspect of complex ions for this chapter is that they form by a Lewis acid-base reaction with the metal being the Lewis acid.
Industry uses large quantities of sodium hydroxide as a cheap, strong base. Sodium chloride is the starting material for the production of NaOH because NaCl is a less expensive starting material than the oxide. Sodium hydroxide is among the top 10 chemicals in production in the United States, and this production was almost entirely by electrolysis of solutions of sodium chloride. This process is the chlor-alkali process, and it is the primary method for producing chlorine.
Sodium hydroxide is an ionic compound and melts without decomposition. It is very soluble in water, giving off a great deal of heat and forming very basic solutions: 40 grams of sodium hydroxide dissolves in only 60 grams of water at 25 °C. Sodium hydroxide is employed in the production of other sodium compounds and is used to neutralize acidic solutions during the production of other chemicals such as petrochemicals and polymers.
Many of the applications of hydroxides are for the neutralization of acids (such as the antacid shown in ) and for the preparation of oxides by thermal decomposition. An aqueous suspension of magnesium hydroxide constitutes the antacid milk of magnesia. Because of its ready availability (from the reaction of water with calcium oxide prepared by the decomposition of limestone, CaCO3), low cost, and activity, calcium hydroxide is used extensively in commercial applications needing a cheap, strong base. The reaction of hydroxides with appropriate acids is also used to prepare salts.

### 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 , occurs in volcanic gases and in the atmosphere near industrial plants that burn fuel containing sulfur compounds.
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  ion or hydrogen sulfite salts containing  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:
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 ), but in the solid state, SO3 exists in several polymeric forms.
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 , are the only commercially important compounds. They are important as bleaching agents (for use with pulp and flour) and for water treatment.

### Nonmetal Oxyacids and Their Salts

Nonmetal oxides form acids when allowed to react with water; these are acid anhydrides. The resulting oxyanions can form salts with various metal ions.

### Nitrogen Oxyacids and Salts

Nitrogen pentaoxide, N2O5, and NO2 react with water to form nitric acid, HNO3. Alchemists, as early as the eighth century, knew nitric acid (shown in ) as aqua fortis (meaning "strong water"). The acid was useful in the separation of gold from silver because it dissolves silver but not gold. Traces of nitric acid occur in the atmosphere after thunderstorms, and its salts are widely distributed in nature. There are tremendous deposits of Chile saltpeter, NaNO3, in the desert region near the boundary of Chile and Peru. Bengal saltpeter, KNO3, occurs in India and in other countries of the Far East.
In the laboratory, it is possible to produce nitric acid by heating a nitrate salt (such as sodium or potassium nitrate) with concentrated sulfuric acid:
The Ostwald process is the commercial method for producing nitric acid. This process involves the oxidation of ammonia to nitric oxide, NO; oxidation of nitric oxide to nitrogen dioxide, NO2; and further oxidation and hydration of nitrogen dioxide to form nitric acid:
Or
Pure nitric acid is a colorless liquid. However, it is often yellow or brown in color because NO2 forms as the acid decomposes. Nitric acid is stable in aqueous solution; solutions containing 68% of the acid are commercially available concentrated nitric acid. It is both a strong oxidizing agent and a strong acid.
The action of nitric acid on a metal rarely produces H2 (by reduction of H+) in more than small amounts. Instead, the reduction of nitrogen occurs. The products formed depend on the concentration of the acid, the activity of the metal, and the temperature. Normally, a mixture of nitrates, nitrogen oxides, and various reduction products form. Less active metals such as copper, silver, and lead reduce concentrated nitric acid primarily to nitrogen dioxide. The reaction of dilute nitric acid with copper produces NO. In each case, the nitrate salts of the metals crystallize upon evaporation of the resultant solutions.
Nonmetallic elements, such as sulfur, carbon, iodine, and phosphorus, undergo oxidation by concentrated nitric acid to their oxides or oxyacids, with the formation of NO2:
Nitric acid oxidizes many compounds; for example, concentrated nitric acid readily oxidizes hydrochloric acid to chlorine and chlorine dioxide. A mixture of one part concentrated nitric acid and three parts concentrated hydrochloric acid (called aqua regia, which means royal water) reacts vigorously with metals. This mixture is particularly useful in dissolving gold, platinum, and other metals that are more difficult to oxidize than hydrogen. A simplified equation to represent the action of aqua regia on gold is:
Nitrates, salts of nitric acid, form when metals, oxides, hydroxides, or carbonates react with nitric acid. Most nitrates are soluble in water; indeed, one of the significant uses of nitric acid is to prepare soluble metal nitrates.
Nitric acid finds extensive use in the laboratory and in chemical industries as a strong acid and strong oxidizing agent. It is important in the manufacture of explosives, dyes, plastics, and drugs. Salts of nitric acid (nitrates) are valuable as fertilizers. Gunpowder is a mixture of potassium nitrate, sulfur, and charcoal.
The reaction of N2O3 with water gives a pale blue solution of nitrous acid, HNO2. However, HNO2 (shown in ) is easier to prepare by the addition of an acid to a solution of nitrite; nitrous acid is a weak acid, so the nitrite ion is basic in aqueous solution:
Nitrous acid is very unstable and exists only in solution. It disproportionates slowly at room temperature (rapidly when heated) into nitric acid and nitric oxide. Nitrous acid is an active oxidizing agent with strong reducing agents, and strong oxidizing agents oxidize it to nitric acid.
Sodium nitrite, NaNO2, is an additive to meats such as hot dogs and cold cuts. The nitrite ion has two functions. It limits the growth of bacteria that can cause food poisoning, and it prolongs the meat’s retention of its red color. The addition of sodium nitrite to meat products is controversial because nitrous acid reacts with certain organic compounds to form a class of compounds known as nitrosamines. Nitrosamines produce cancer in laboratory animals. This has prompted the FDA to limit the amount of NaNO2 in foods.
The nitrites are much more stable than the acid, but nitrites, like nitrates, can explode. Nitrites, like nitrates, are also soluble in water (AgNO2 is only slightly soluble).

### Phosphorus Oxyacids and Salts

Pure orthophosphoric acid, H3PO4 (shown in ), forms colorless, deliquescent crystals that melt at 42 °C. The common name of this compound is phosphoric acid, and is commercially available as a viscous 82% solution known as syrupy phosphoric acid. One use of phosphoric acid is as an additive to many soft drinks.
One commercial method of preparing orthophosphoric acid is to treat calcium phosphate rock with concentrated sulfuric acid:
Dilution of the products with water, followed by filtration to remove calcium sulfate, gives a dilute acid solution contaminated with calcium dihydrogen phosphate, Ca(H2PO4)2, and other compounds associated with calcium phosphate rock. It is possible to prepare pure orthophosphoric acid by dissolving P4O10 in water.
The action of water on P4O6, PCl3, PBr3, or PI3 forms phosphorous acid, H3PO3 (shown in ). The best method for preparing pure phosphorous acid is by hydrolyzing phosphorus trichloride:
Heating the resulting solution expels the hydrogen chloride and leads to the evaporation of water. When sufficient water evaporates, white crystals of phosphorous acid will appear upon cooling. The crystals are deliquescent, very soluble in water, and have an odor like that of garlic. The solid melts at 70.1 °C and decomposes at about 200 °C by disproportionation into phosphine and orthophosphoric acid:
Phosphorous acid forms only two series of salts, which contain the dihydrogen phosphite ion,  or the hydrogen phosphate ion,  respectively. It is not possible to replace the third atom of hydrogen because it is not very acidic, as it is not easy to ionize the P-H bond.

### Sulfur Oxyacids and Salts

The preparation of sulfuric acid, H2SO4 (shown in ), begins with the oxidation of sulfur to sulfur trioxide and then converting the trioxide to sulfuric acid. Pure sulfuric acid is a colorless, oily liquid that freezes at 10.5 °C. It fumes when heated because the acid decomposes to water and sulfur trioxide. The heating process causes the loss of more sulfur trioxide than water, until reaching a concentration of 98.33% acid. Acid of this concentration boils at 338 °C without further change in concentration (a constant boiling solution) and is commercially concentrated H2SO4. The amount of sulfuric acid used in industry exceeds that of any other manufactured compound.
The strong affinity of concentrated sulfuric acid for water makes it a good dehydrating agent. It is possible to dry gases and immiscible liquids that do not react with the acid by passing them through the acid.
Sulfuric acid is a strong diprotic acid that ionizes in two stages. In aqueous solution, the first stage is essentially complete. The secondary ionization is not nearly so complete, and  is a moderately strong acid (about 25% ionized in solution of a  salt: Ka = 1.2  10−2).
Being a diprotic acid, sulfuric acid forms both sulfates, such as Na2SO4, and hydrogen sulfates, such as NaHSO4. Most sulfates are soluble in water; however, the sulfates of barium, strontium, calcium, and lead are only slightly soluble in water.
Among the important sulfates are Na2SO4⋅10H2O and Epsom salts, MgSO4⋅7H2O. Because the  ion is an acid, hydrogen sulfates, such as NaHSO4, exhibit acidic behavior, and this compound is the primary ingredient in some household cleansers.
Hot, concentrated sulfuric acid is an oxidizing agent. Depending on its concentration, the temperature, and the strength of the reducing agent, sulfuric acid oxidizes many compounds and, in the process, undergoes reduction to SO2,   S, H2S, or S2−.
Sulfur dioxide dissolves in water to form a solution of sulfurous acid, as expected for the oxide of a nonmetal. Sulfurous acid is unstable, and it is not possible to isolate anhydrous H2SO3. Heating a solution of sulfurous acid expels the sulfur dioxide. Like other diprotic acids, sulfurous acid ionizes in two steps: The hydrogen sulfite ion,  and the sulfite ion,  form. Sulfurous acid is a moderately strong acid. Ionization is about 25% in the first stage, but it is much less in the second (Ka1 = 1.2  10−2 and Ka2 = 6.2  10−8).
In order to prepare solid sulfite and hydrogen sulfite salts, it is necessary to add a stoichiometric amount of a base to a sulfurous acid solution and then evaporate the water. These salts also form from the reaction of SO2 with oxides and hydroxides. Heating solid sodium hydrogen sulfite forms sodium sulfite, sulfur dioxide, and water:
Strong oxidizing agents can oxidize sulfurous acid. Oxygen in the air oxidizes it slowly to the more stable sulfuric acid:
Solutions of sulfites are also very susceptible to air oxidation to produce sulfates. Thus, solutions of sulfites always contain sulfates after exposure to air.

### Halogen Oxyacids and Their Salts

The compounds HXO, HXO2, HXO3, and HXO4, where X represents Cl, Br, or I, are the hypohalous, halous, halic, and perhalic acids, respectively. The strengths of these acids increase from the hypohalous acids, which are very weak acids, to the perhalic acids, which are very strong.  lists the known acids, and, where known, their pKa values are given in parentheses.
The only known oxyacid of fluorine is the very unstable hypofluorous acid, HOF, which is prepared by the reaction of gaseous fluorine with ice:
The compound is very unstable and decomposes above −40 °C. This compound does not ionize in water, and there are no known salts. It is uncertain whether the name hypofluorous acid is even appropriate for HOF; a more appropriate name might be hydrogen hypofluorite.
The reactions of chlorine and bromine with water are analogous to that of fluorine with ice, but these reactions do not go to completion, and mixtures of the halogen and the respective hypohalous and hydrohalic acids result. Other than HOF, the hypohalous acids only exist in solution. The hypohalous acids are all very weak acids; however, HOCl is a stronger acid than HOBr, which, in turn, is stronger than HOI.
The addition of base to solutions of the hypohalous acids produces solutions of salts containing the basic hypohalite ions, OX−. It is possible to isolate these salts as solids. All of the hypohalites are unstable with respect to disproportionation in solution, but the reaction is slow for hypochlorite. Hypobromite and hypoiodite disproportionate rapidly, even in the cold:
Sodium hypochlorite is an inexpensive bleach (Clorox) and germicide. The commercial preparation involves the electrolysis of cold, dilute, aqueous sodium chloride solutions under conditions where the resulting chlorine and hydroxide ion can react. The net reaction is:
The only definitely known halous acid is chlorous acid, HClO2, obtained by the reaction of barium chlorite with dilute sulfuric acid:
Filtering the insoluble barium sulfate leaves a solution of HClO2. Chlorous acid is not stable; it slowly decomposes in solution to yield chlorine dioxide, hydrochloric acid, and water. Chlorous acid reacts with bases to give salts containing the chlorite ion (shown in ). Sodium chlorite finds an extensive application in the bleaching of paper because it is a strong oxidizing agent and does not damage the paper.
Chloric acid, HClO3, and bromic acid, HBrO3, are stable only in solution. The reaction of iodine with concentrated nitric acid produces stable white iodic acid, HIO3:
It is possible to obtain the lighter halic acids from their barium salts by reaction with dilute sulfuric acid. The reaction is analogous to that used to prepare chlorous acid. All of the halic acids are strong acids and very active oxidizing agents. The acids react with bases to form salts containing chlorate ions (shown in ). Another preparative method is the electrochemical oxidation of a hot solution of a metal halide to form the appropriate metal chlorates. Sodium chlorate is a weed killer; potassium chlorate is used as an oxidizing agent.
Perchloric acid, HClO4, forms when treating a perchlorate, such as potassium perchlorate, with sulfuric acid under reduced pressure. The HClO4 can be distilled from the mixture:
Dilute aqueous solutions of perchloric acid are quite stable thermally, but concentrations above 60% are unstable and dangerous. Perchloric acid and its salts are powerful oxidizing agents, as the very electronegative chlorine is more stable in a lower oxidation state than 7+. Serious explosions have occurred when heating concentrated solutions with easily oxidized substances. However, its reactions as an oxidizing agent are slow when perchloric acid is cold and dilute. The acid is among the strongest of all acids. Most salts containing the perchlorate ion (shown in ) are soluble. It is possible to prepare them from reactions of bases with perchloric acid and, commercially, by the electrolysis of hot solutions of their chlorides.
Perbromate salts are difficult to prepare, and the best syntheses currently involve the oxidation of bromates in basic solution with fluorine gas followed by acidification. There are few, if any, commercial uses of this acid or its salts.
There are several different acids containing iodine in the 7+-oxidation state; they include metaperiodic acid, HIO4, and paraperiodic acid, H5IO6. These acids are strong oxidizing agents and react with bases to form the appropriate salts.

### Key Concepts and Summary

Oxygen is one of the most reactive elements. This reactivity, coupled with its abundance, makes the chemistry of oxygen very rich and well understood.
Compounds of the representative metals with oxygen exist in three categories (1) oxides, (2) peroxides and superoxides, and (3) hydroxides. Heating the corresponding hydroxides, nitrates, or carbonates is the most common method for producing oxides. Heating the metal or metal oxide in oxygen may lead to the formation of peroxides and superoxides. The soluble oxides dissolve in water to form solutions of hydroxides. Most metals oxides are base anhydrides and react with acids. The hydroxides of the representative metals react with acids in acid-base reactions to form salts and water. The hydroxides have many commercial uses.
All nonmetals except fluorine form multiple oxides. Nearly all of the nonmetal oxides are acid anhydrides. The acidity of oxyacids requires that the hydrogen atoms bond to the oxygen atoms in the molecule rather than to the other nonmetal atom. Generally, the strength of the oxyacid increases with the number of oxygen atoms bonded to the nonmetal atom and not to a hydrogen.

### Chemistry End of Chapter Exercises