Deuterium
Deuterium is one of two stable isotopes of hydrogen; the other is protium, or hydrogen-1, H. The deuterium nucleus contains one proton and one neutron, whereas the far more common H has no neutrons.
The name deuterium comes from Greek deuteros, meaning "second". American chemist Harold Urey discovered deuterium in 1931. Urey and others produced samples of heavy water in which the H had been highly concentrated. The discovery of deuterium won Urey a Nobel Prize in 1934.
Nearly all deuterium found in nature was synthesized in the Big Bang 13.8 billion years ago, forming the primordial ratio of H to H. Deuterium is subsequently produced by the slow stellar proton–proton chain, but rapidly destroyed by exothermic fusion reactions. The deuterium–deuterium reaction has the second-lowest energy threshold, and is the most astrophysically accessible, occurring in both stars and brown dwarfs.
The gas giant planets display the primordial ratio of deuterium. Comets show an elevated ratio similar to Earth's oceans. This reinforces theories that much of Earth's ocean water is of cometary origin. The deuterium ratio of comet 67P/Churyumov–Gerasimenko, as measured by the Rosetta space probe, is about three times that of Earth water. This figure is the highest yet measured in a comet, thus deuterium ratios continue to be an active topic of research in both astronomy and climatology.
Deuterium is used in most nuclear weapons, many fusion power experiments, and as the most effective neutron moderator, primarily in heavy water nuclear reactors. It is also used as an isotopic label, in biogeochemistry, NMR spectroscopy, and deuterated drugs.
Differences from common hydrogen (protium)
Chemical symbol
Deuterium is often represented by the chemical symbol D. Since it is an isotope of hydrogen with mass number 2, it is also represented by H. IUPAC allows both D and H, though H is preferred. A distinct chemical symbol is used for convenience because of the isotope's common use in various scientific processes. Also, its large mass difference with protium confers non-negligible chemical differences with H compounds. Deuterium has a mass of, about twice the mean hydrogen atomic weight of, or twice protium's mass of. The isotope weight ratios within other elements are largely insignificant in this regard.Spectroscopy
In quantum mechanics, the energy levels of electrons in atoms depend on the reduced mass of the system of electron and nucleus. For a hydrogen atom, the role of reduced mass is most simply seen in the Bohr model of the atom, where the reduced mass appears in a simple calculation of the Rydberg constant and Rydberg equation, but the reduced mass also appears in the Schrödinger equation, and the Dirac equation for calculating atomic energy levels.The reduced mass of the system in these equations is close to the mass of a single electron, but differs from it by a small amount about equal to the ratio of mass of the electron to the nucleus. For H, this amount is about, or 1.000545, and for H it is even smaller:, or 1.000272. The energies of electronic spectra lines for H and H therefore differ by the ratio of these two numbers, which is 1.000272. The wavelengths of all deuterium spectroscopic lines are shorter than the corresponding lines of light hydrogen, by 0.0272%. In astronomical observation, this corresponds to a blue Doppler shift of 0.0272% of the speed of light, or 81.6 km/s.
The differences are much more pronounced in vibrational spectroscopy such as infrared spectroscopy and Raman spectroscopy, and in rotational spectra such as microwave spectroscopy because the reduced mass of the deuterium is markedly higher than that of protium. In nuclear magnetic resonance spectroscopy, deuterium has a very different NMR frequency and is much less sensitive. Deuterated solvents are usually used in protium NMR to prevent the solvent from overlapping with the signal, though deuterium NMR in its own right is also possible.
Big Bang nucleosynthesis
Synthesis during the formation of the universe is the only significant way naturally occurring deuterium has been created; it is destroyed in stellar fusion. Deuterium is thought to have played an important role in setting the number and ratios of the elements that were formed in the Big Bang. Combining thermodynamics and the changes brought about by cosmic expansion, one can calculate the fraction of protons and neutrons based on the temperature at the point that the universe cooled enough to allow formation of nuclei. This calculation indicates seven protons for every neutron at the beginning of nucleogenesis, a ratio that would remain stable even after nucleogenesis was over. This fraction was in favor of protons initially, primarily because the lower mass of the proton favored their production. As the Universe expanded, it cooled. Free neutrons and protons are less stable than helium nuclei, and the protons and neutrons had a strong energetic reason to form helium-4. However, forming helium-4 requires the intermediate step of forming deuterium.Through much of the few minutes after the Big Bang during which nucleosynthesis could have occurred, the temperature was high enough that the mean energy per particle was greater than the binding energy of weakly bound deuterium; therefore, any deuterium that was formed was immediately destroyed. This situation is known as the deuterium bottleneck. The bottleneck delayed formation of any helium-4 until the Universe became cool enough to form deuterium. At this point, there was a sudden burst of element formation. However, very soon thereafter, at twenty minutes after the Big Bang, the Universe became too cool for any further nuclear fusion or nucleosynthesis. At this point, the elemental abundances were nearly fixed, with the only change as some of the radioactive products of Big Bang nucleosynthesis decay. The deuterium bottleneck in the formation of helium, together with the lack of stable ways for helium to combine with hydrogen or with itself meant that an insignificant amount of carbon, or any elements heavier than carbon, formed in the Big Bang. These elements thus required formation in stars. At the same time, the failure of much nucleogenesis during the Big Bang ensured that there would be plenty of hydrogen in the later universe available to form long-lived stars, such as the Sun.
Abundance
Deuterium occurs in trace amounts naturally as deuterium gas, but most deuterium in the Universe is bonded with H to form a gas called hydrogen deuteride. Similarly, natural water contains deuterated molecules, almost all as semiheavy water HDO with only one deuterium.The existence of deuterium on Earth, elsewhere in the Solar System, and in the spectra of stars, is also an important datum in cosmology. Gamma radiation from ordinary nuclear fusion dissociates deuterium into protons and neutrons, and there is no known natural process other than Big Bang nucleosynthesis that might have produced deuterium at anything close to its observed natural abundance. Deuterium is produced by the rare cluster decay, and occasional absorption of naturally occurring neutrons by light hydrogen, but these are trivial sources. There is thought to be little deuterium in the interior of the Sun and other stars, as at these temperatures the nuclear fusion reactions that consume deuterium happen much faster than the proton–proton reaction that creates deuterium. However, deuterium persists in the outer solar atmosphere at roughly the same concentration as in Jupiter, and this has probably been unchanged since the origin of the Solar System. The natural abundance of H seems to be a very similar fraction of hydrogen, wherever hydrogen is found, unless there are obvious processes at work that concentrate it.
The existence of deuterium at a low but constant primordial fraction in all hydrogen is another one of the arguments in favor of the Big Bang over the Steady State theory of the Universe. The observed ratios of hydrogen to helium to deuterium in the universe are difficult to explain except with a Big Bang model. It is estimated that the abundances of deuterium have not evolved significantly since their production about 13.8 billion years ago. Measurements of Milky Way galactic deuterium from ultraviolet spectral analysis show a ratio of as much as 23 atoms of deuterium per million hydrogen atoms in undisturbed gas clouds, which is only 15% below the WMAP estimated primordial ratio of about 27 atoms per million from the Big Bang. This has been interpreted to mean that less deuterium has been destroyed in star formation in the Milky Way galaxy than expected, or perhaps deuterium has been replenished by a large in-fall of primordial hydrogen from outside the galaxy. In space a few hundred light years from the Sun, deuterium abundance is only 15 atoms per million, but this value is presumably influenced by differential adsorption of deuterium onto carbon dust grains in interstellar space.
The abundance of deuterium in Jupiter's atmosphere has been directly measured by the Galileo space probe as 26 atoms per million hydrogen atoms. ISO-SWS observations find 22 atoms per million hydrogen atoms in Jupiter, and this abundance is thought to represent close to the primordial Solar System ratio. This is about 17% of the terrestrial ratio of 156 deuterium atoms per million hydrogen atoms.
Comets such as Comet Hale–Bopp and Halley's Comet have been measured to contain more deuterium, ratios which are enriched with respect to the presumed protosolar nebula ratio, probably due to heating, and which are similar to the ratios found in Earth seawater. The recent measurement of deuterium amounts of 161 atoms per million hydrogen in Comet 103P/Hartley, a ratio almost exactly that in Earth's oceans, emphasizes the theory that Earth's surface water may be largely from comets. Most recently the HHR of 67P/Churyumov–Gerasimenko as measured by Rosetta is about three times that of Earth water. This has caused renewed interest in suggestions that Earth's water may be partly of asteroidal origin.
Deuterium has also been observed to be concentrated over the mean solar abundance in other terrestrial planets, in particular Mars and Venus.