OXYGEN
| Physical Properties |
Atomic Number: 8
Mass Number: 15.9994
Electron Configuration: 1s22s22p4
Boiling Point:-183oC
Melting Point: -218.4oC
First Ionization Energy: 1314 kJ/mol
Atomic Radius: 74 pm
Ionic Radius: 140 (O2-)
Electronegativity: 3.4
| Isotopes of Oxygen |
Oxygen exists as three isotopes as summarized below. By far the most common isotope is 16O. The second, 17O, is NMR active and has a nuclear spin of 5/2. The third isotope, 18O, is commonly used as a nonradioactive `tracer for the element.
| 16O | 99.759% |
| 17O | 0.0374% |
| 18O | 0.2039% |
| Allotropes of Oxygen |
A an element, oxygen occurs as a diatomic element in which the oxygen atoms are connected by a double bond. The bond distance is 121 pm. Oxygen gas is colorless and odorless, but is pale blue in color as a liquid. Oxygen is paramagnetic, a property which can only be explained through molecular orbital theory. Oxygen combines with nearly all other elements on the periodic table. Oxygen will react with most metals to form oxides, with hydrogen to form water, and with nonmetals such as sulfur and fluorine. Oxygen is the second most electronegative element on the periodic table, next to fluorine. In most covalent bonds with oxygen the bonding electrons are sharred unequally, resulting in a partial negative charge on the oxygen atom and a partial positive charge on the bonded atom.
A second form of oxygen is the element ozone, which consists of triatomic molecules The two oxygen-oxygen bonds of the ozone molecule are the same and have a length of 128 pm. The longer bond length represents a lower bond order than in the oxygen diatomic molecule. As might be expected due to the heavier molecular weight, ozone boils at a higher temperature than molecular oxygen. Ozone molecules have a bent shape, a property which could be predicted from the dot structure. Unlike oxygen, ozone has a pungent odor. Ozone is much more chemically reactive than oxygen. Diatomic oxygen and ozone are examples of allotropes, or different forms of the same element.
| |
Molecular Formula | Molecular Shape | Bond Length | Boiling Point |
| Oxygen | O2 | Linear | 121 pm | -183oC |
| Ozone | O3 | Bent | 128 pm | -112oC |
| Oxide, Peroxide, and Superoxide ions |
As one might predict by the position of oxygen on the
periodic table, oxgen can gain two additional oxygen atoms to form the
oxide ion, and many compounds containing the oxide ion are known. Oxygen
also forms the peroxide and superoxide ions. The formulas for these species
are listed in the table below. The peroxide can be viewed as an oxygen
molcule with two extra electrons. According to molecular orbital theory,
these two electrons go into antibonding orbitals, reducing the bond order
to one. Metals that can form ionic peroxides include the alkali metals,
calcium, barium, and strintium. The superoxide molecule can be viewed as
an oxygen molecule with an extra single electron and has a bond order of
one and a half. Metals that can form ionic superoxides include potassium,
rubidium, and cesium.
| Formula | Bond Order | Bond Length | Examples | |
| Oxide | O2- | n/a | n/a | MgO, CaO |
| Peroxide | O22- | 1 | 149 pm | H2O2, Na2O2, K2O2, BaO2 |
| Superoxide | O2- | 1.5 | 134 pm | KO2, RbO2, CsO2 |
Magnesium, calcium, strontium, and barium oxides adopt a
rock-salt structure, in which the oxide ions form a face-centered cubic
array and the metal ions fill the octahedral holes. Lithium, sodium, and
potassium oxides, in contrast, adopt the antifluorite structure. In this
type of structure, the oxide ions form a face-centered cubic array and
the metal ions fill half the tetrahedral holes. This is considered to be
the inverse of the fluorite structure, where the cations form the face-centered
cubic array and the anions fit into the tetrahedral holes.
| Rock-Salt Structure | MgO, CaO, SrO, BaO |
| Antifluorite Structure | Li2O, Na2O, K2O |
| Wurtzite Structure | ZnO |
| Molecular Compounds of Oxygen |
Compounds with Hydrogen
Hydrogen peroxide is a colorless, viscous liquid with
a melting point of - 0.41 C and a boiling point of 150.2 C. Dilute solutions
of hydrogen peroxide (approximately 3%) are commonly used as an antiseptic.
Hydrogen peroxide is unstable and decomposes to give water and oxygen;
this serves as a potential laboratory preparation of oxygen. The decomposition
is catalyzed by manganese dioxide, as well as several other metal ions.
Hydrogen peroxide is a strong oxidizing agent, and will oxidize the iodide
ion to iodine. In alkaline solution, hydrogen peroxide can also serve as
a mild reducing agent.
| Formula | Name | Melting Point | Boiling Point | Density |
| H2O | Water | 0.00oC | 100.0oC | 1.0 g/mL |
| H2O2 | Hydrogen Peroxide | -0.41oC | 150.2oC | 1.4 g/mL |
Compounds with Sulfur
The two most common molecular compounds between sulfur and oxygen are
sulfur dioxode and sulfur trioxide. Sulfur dioxide has a boiling point
of -10 C and is a melting point of -75.5 C. It has a pungent, choking odor
and is the product formed when sulfur burns. Like ozone, the sulfur dioxide
molecule has an angular shape, and the the bond angle is 119 degrees. Liquid
sulfur dioxide is a good solvent. Sulfur dioxide dissolves in water to
produce sulfurous acid, a weak diprotic acid.
Sulfur trioxide is formed from the oxidation of sulfur
dioxide. In this particular molecule, the sulfur is the central atom and
supports an expanded octet. Sulfur trioxide has a melting point of 16.9
C and a boiling point of 44.6 C. Sulfur trioxide reacts vigorously with
water to produce sulfuric acid.
| Formula | Name | Melting Point | Boiling Point |
| SO2 | Sulfur Dioxide | -75.5oC | -10oC |
| SO3 | Sulfur Trioxide | 16.9oC | 44.6oC |
Compounds with Carbon
Two common compounds are carbon dioxide and carbon monoxide. Carbon
dioxide is produced in vast quantities by combustion of carbon-containing
molecules. Carbon dioxide is a colorless, odorless gas. In the carbon dioxide
molecule, both carbon-oxygen bonds are double bonds and the shape of the
molecule is linear. Dry ice is composed of solid carbon dioxide. Dry ice
sublimes, or passes from a solid directly to a gas, at -78.5 C.
Carbon monoxide is often formed when carbon-containing
molecules are burned in a limited supply of oxygen. Carbon monoxide has
a boiling point of -190 C and is a gas at room temperature. In the carbon
monoxide molecule, the atoms are joined by a triple bond. Carbon monoxide
is highly toxic because it is absorbed by hemoglobin many times better
than oxygen, tying up the hemoglobin so that it can no longer combine wtih
oxygen.
| Formula | Name | Comments |
| CO | Carbon Monoxide | boiling point -190oC |
| CO2 | Carbon Dioxide | sublimes at -78.5oC |
Compounds with Nitrogen
Oxygen forms an entire series of molecular compounds with nitrogen. Some properties of these compounds are summarized below.
| Formula | Name | Comments |
| N2O | Nitrous Oxide | melting point is -90.9oC, boiling point is
-88.5oC linear molecule |
| NO | Nitric Oxide | odd-electron species bond order 2.5 |
| NO2 | Nitrogen Dioxide | odd-electron species shape is bent brown gas at room temperature exists in equilibrium with N2O4 |
| N2O3 | Dinitrogen Trioxide | anhydride of nitrous acid intensely-colored blue liquid or pale blue solid |
| N2O4 | Dinitrogen Tetroxide | melting point -11.2oC, boiling point 21.15oC solid is colorless exists in equilibrium with NO2 |
| N2O5 | Dinitrogen Pentoxide | anhydride of nitric acid unstable, colorless crystals |
| Oxoanions |
In addition to the molecular compounds listed above, oxygen forms an extensive series of oxoanions with many of the nonmetals. The chemical formulas and names of some nitrogen, oxygen, and chlorine oxoanions are listed in the table below.
| NO2- | Nitrite | SO42- | Sulfate | ClO- | Hypochlorite |
| NO3- | Nitrate | SO32- | Sulfite | ClO2- | Chlorite |
| N2O2- | Hyponitrate | S2O32- | Thiosulfate | ClO3- | Chlorate |
| NO43- | Orthonitrate | S2O42- | Dithionate | ClO4- | Perchlorate |
| S2O82- | Peroxydisulfate |
| Reactions of Molecular Oxygen |
Oxygen is highly reactive. Metals tend to react with oxygen to form oxides. For example, magnesium burns with a brilliant flame in oxygen to produce magnesium oxide. Sulfur burns with a blue flame in oxygen to produce sulfur dioxide.