Properties and molecular structure to each other. The bond can be variously described based on level of theory, but is reasonably and simply described as a covalent
double bond that results from the filling of
molecular orbitals formed from the
atomic orbitals of the individual oxygen atoms, the filling of which results in a
bond order of two. More specifically, the double bond is the result of sequential, low-to-high energy, or
Aufbau, filling of orbitals, and the resulting cancellation of contributions from the 2s electrons, after sequential filling of the low σ and σ* orbitals; σ overlap of the two atomic 2p orbitals that lie along the O–O molecular axis and π overlap of two pairs of atomic 2p orbitals perpendicular to the O–O molecular axis, and then cancellation of contributions from the remaining two 2p electrons after their partial filling of the π* orbitals. This combination of cancellations and σ and π overlaps results in dioxygen's double-bond character and reactivity, as well as the presence of a triplet electronic
ground state. An
electron configuration with two unpaired electrons, as is found in dioxygen orbitals (see the filled π* orbitals in the diagram), that are of equal energy—i.e.,
degenerate—is a configuration termed a
spin triplet state. Hence, the ground state of the molecule is referred to as
triplet oxygen. The highest-energy, partially filled orbitals are
antibonding, and so their filling weakens the bond order from three to two. Because of its unpaired electrons, triplet oxygen reacts only slowly with most organic molecules, which have paired electron spins; this prevents spontaneous combustion. In the triplet form, molecules are
paramagnetic. That is, they impart magnetic character to oxygen when it is in the presence of a magnetic field, because of the
spin of the unpaired electrons in the molecule and the negative
exchange energy between neighboring molecules. Oxygen's paramagnetism can be used in paramagnetic oxygen gas analysers that determine gaseous oxygen concentration, especially in industrial process control and medicine.
Singlet oxygen is a name given to several higher-energy species of molecular in which all the electron spins are paired. It is much more reactive with common
organic molecules than normal (triplet) molecular oxygen. In nature, singlet oxygen is commonly formed from water during photosynthesis, using the energy of sunlight. It is also produced in the
troposphere by the photolysis of ozone by light of short wavelength and by the
immune system as a source of active oxygen.
Carotenoids in photosynthetic organisms (and possibly animals) play a major role in absorbing energy from singlet oxygen and converting it to the unexcited ground state before it can cause harm to tissues.
Allotropes representation of dioxygen (O2) molecule The common
allotrope of elemental oxygen on Earth is called
dioxygen, , the allotrope that is major part of the Earth's atmospheric oxygen (see
occurrence). O2 has a bond length of 121
pm and a bond energy of 498
kJ/mol. Trioxygen () is usually known as
ozone and is a very reactive allotrope of oxygen that is damaging to lung tissue. Ozone is produced in the
upper atmosphere when combines with atomic oxygen made by the splitting of by
ultraviolet (UV) radiation. The
metastable molecule
tetraoxygen () was discovered in 2001 and was assumed to exist in one of the six phases of
solid oxygen. In 2006, this phase, created by pressurizing to 20
GPa, was shown to form a
rhombohedral cluster. This cluster has the potential to be a much more powerful
oxidizer than either or and may therefore be used in
rocket fuel.
Physical properties Oxygen
dissolves more readily in water than nitrogen does. Water in equilibrium with air contains approximately 1 molecule of dissolved for every 2 molecules of (1:2), compared with an atmospheric ratio of approximately 1:4. The solubility of oxygen in water is temperature-dependent, and about twice as much () dissolves at than at (). At and in air, freshwater can dissolve about 6.04
milliliters (mL) of oxygen per
liter, while
seawater contains about 4.95 mL per liter. At the solubility increases to 9.0 mL (50% more than at ) per liter for freshwater and 7.2 mL (45% more) per liter for sea water. Oxygen condenses at 90.20
K (−182.95 °C, −297.31 °F) and freezes at 54.36 K (−218.79 °C, −361.82 °F). Both
liquid and
solid are clear substances with a light
sky-blue color caused by absorption in the red (in contrast with the blue color of the sky, which is due to
Rayleigh scattering of blue light). High-purity liquid is usually obtained by the
fractional distillation of liquefied air. Liquid oxygen may also be condensed from air using
liquid nitrogen as a coolant. Liquid oxygen is a highly reactive substance and must be segregated from combustible materials. The absorption in the
Herzberg continuum and
Schumann–Runge bands in the ultraviolet produces atomic oxygen that is important in the chemistry of the middle atmosphere. Excited-state singlet molecular oxygen is responsible for red chemiluminescence in solution. Table of thermal and physical properties of oxygen (O2) at atmospheric pressure:
Isotopes and stellar origin Naturally occurring oxygen is composed of three stable
isotopes,
16O,
17O, and
18O, with 16O being the most abundant (99.762%
natural abundance). 16O is one of the dominant fusion products in massive
stars. It is
synthesized at the end of the
triple-alpha process with some synthesis in the
neon burning process. Both 17O and 18O require seed nuclei. 17O is primarily made by the burning of hydrogen into
helium during the
CNO cycle, making it a common isotope in the hydrogen burning zones of stars. The most stable are 15O with a
half-life of 122.24 seconds and 14O with a half-life of 70.606 seconds.
Occurrence Oxygen is the third most abundant chemical element in the universe, after hydrogen and helium. About 0.9% of the
Sun's mass is oxygen. It is also the major component of the world's oceans (88.8% by mass). Earth is unusual among the planets of the
Solar System in having such a high concentration of oxygen gas in its atmosphere.
Mars (with 0.1% by volume) and
Venus have much less. The surrounding those planets is produced solely by the action of ultraviolet radiation on oxygen-containing molecules such as carbon dioxide. The unusually high concentration of oxygen gas on Earth is the result of the
oxygen cycle. This
biogeochemical cycle describes the movement of oxygen within and between its three main reservoirs on Earth: the atmosphere, the biosphere, and the
lithosphere. The main driving factor of the oxygen cycle is
photosynthesis, which is responsible for modern Earth's atmosphere. Photosynthesis releases oxygen into the atmosphere, while
respiration,
decay, and combustion remove it from the atmosphere. In the present equilibrium, production and consumption occur at the same rate. Free oxygen also occurs in solution in the world's water bodies. The increased solubility of at lower temperatures (see
Physical properties) has important implications for ocean life, as polar oceans support a much higher density of life due to their higher oxygen content. Scientists assess this aspect of water quality by measuring the water's
biochemical oxygen demand, or the amount of needed to restore it to a normal concentration. Significant deoxygenation has been observed in tropical oceans. Warming oceans' waters are expected to lose oxygen over the next century and into the future for a thousand years; the possible consequences include minimal oxygen zones which are unable to support
macrofauna.
Analysis vs. 18O|alt=Time evolution of oxygen-18 concentration on the scale of 500 million years showing many local peaks.
Paleoclimatologists measure the ratio of oxygen-18 and oxygen-16 in the
shells and
skeletons of marine organisms to determine the climate millions of years ago (see
oxygen isotope ratio cycle).
Seawater molecules that contain the lighter
isotope, oxygen-16, evaporate at a slightly faster rate than water molecules containing the 12% heavier oxygen-18, and this disparity increases at lower temperatures. During periods of lower global temperatures, snow and rain from that evaporated water tends to be higher in oxygen-16, and the seawater left behind tends to be higher in oxygen-18. Marine organisms then incorporate more oxygen-18 into their skeletons and shells than they would in a warmer climate.
Planetary geologists have measured the relative quantities of oxygen isotopes in samples from the
Earth, the
Moon,
Mars, and
meteorites, but were long unable to obtain reference values for the isotope ratios in the
Sun, believed to be the same as those of the
primordial solar nebula. Analysis of a
silicon wafer exposed to the
solar wind in space and returned by the crashed
Genesis spacecraft has shown that the Sun has a higher proportion of oxygen-16 than does the Earth. The measurement implies that an unknown process depleted oxygen-16 from the Sun's
disk of protoplanetary material prior to the coalescence of dust grains that formed the Earth. Oxygen presents two spectrophotometric
absorption bands peaking at wavelengths of 687 and 760
nm. Some
remote sensing scientists have proposed using the measurement of the radiance coming from vegetation canopies in those bands to characterize plant health status from a
satellite platform. This approach exploits the fact that in those bands it is possible to discriminate the vegetation's
reflectance from its
fluorescence, which is much weaker. The measurement is technically difficult owing to the low
signal-to-noise ratio and the physical structure of vegetation; but it has been proposed as a possible method of monitoring the
carbon cycle from satellites on a global scale. ==Biological production and role of O2==