heavy water

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Deuterium Monoxide
IUPAC name	[2H]2-water
Other names	Water-d2 Heavy water Dideuterium monoxide
Identifiers
CAS number	7789-20-0 Y
ChEBI	41981
RTECS number	ZC0230000
ChemSpider ID	23004
Properties
Molecular formula	D2O
Molar mass	20.04 g/mol
Appearance	transparent, colorless liquid
Density	1.1056 g/mL, liquid (20°C) 1.0177 g/cm3, solid (at m.p)
Melting point	3.82 °C, 38.88 °F (276.97 K)
Boiling point	101.4 °C, 214.56 °F (374.55 K)
Viscosity	0.00125 Pa·s at 20 °C
Dipole moment	1.87 D
Hazards
MSDS	External MSDS
NFPA 704	0 1 1
Y (what is this?)  (verify) Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa)
Infobox references

Heavy water is water that contains a higher proportion than normal of the isotope deuterium, as deuterium oxide, D₂O or ²H₂O, or as deuterium protium oxide, HDO or ¹H²HO.^[1] Its physical and chemical properties are somewhat similar to those of water, H₂O. The ratio of deuterium to hydrogen in normal water is about 156ppm (see Vienna Standard Mean Ocean Water).

Heavy water may contain as much as 100% D₂O, and usually the term refers to water that is highly enriched in deuterium. The isotopic substitution with deuterium alters the bond energy of the hydrogen-oxygen bond in water, altering the physical, chemical, and especially biological properties of the pure or highly-enriched substance to a larger degree than is found in most isotope-substituted chemical compounds.

Relatively pure heavy water was produced in 1933, soon after the discovery of deuterium, the stable heavy isotope of hydrogen. With the discovery of nuclear fission in late 1938 and the need for a neutron moderator which captured few neutrons, heavy water soon achieved importance in relation to early nuclear programs during World War II. Due in part to German reliance on scarce heavy water for reactor research in this war, Germany did not succeed in producing a functioning reactor during World War II. Since this war, heavy water has played a part in a number of reactor designs, both in designs for power and for nuclear weapon-making. Reactors which use enriched uranium are able to use normal “light water” for neutron moderation, and remain the most common type of reactor in use today.

Heavy water is not radioactive, and has physical properties similar to water save for being about 11% more dense. As commercially made, heavy water contains whatever tritium was present in the water from which it was isolated. When the water in eukaryotic organisms is replaced by more than about 25 to 50% heavy water, they experience toxicity due to interference by the deuterium with the mitotic apparatus of these cells. Higher organisms, including mammals, if given only heavy water, soon become ill and die at the point that about half their body water has been replaced. Bacteria are able to grow slowly in pure heavy water.

Small concentrations of heavy water are nontoxic. The adult human body naturally contains deuterium equivalent to the amount in about 5 grams of heavy water, and comparable doses of heavy water are still used as safe non-radioactive tracers for metabolic experiments in humans and other animals.

Other meanings

Semiheavy water

Semiheavy water, HDO, exists whenever there is water with hydrogen-1 (or protium) and deuterium present in the mixture. This is because hydrogen atoms (hydrogen-1 and deuterium) are rapidly exchanged between water molecules. Water containing 50% H and 50% D in its hydrogen actually contains about 50% HDO and 25% each of H₂O and D₂O, in dynamic equilibrium. Semiheavy water, HDO, occurs naturally in regular water at a proportion of about 1 molecule in 3,200 (each hydrogen has a probability of 1 in 6,400 of being D). Heavy water, D₂O, by comparison, occurs naturally at a proportion of about 1 molecule in 41 million (i.e., 1 in 6,400²). This makes semiheavy water far more prevalent than 'normal' heavy water.

Heavy-oxygen water

A common type of heavy-oxygen water H₂¹⁸O is available commercially for use as a non-radioactive isotopic tracer (see doubly-labeled water for discussion), and qualifies as "heavy water" insofar as having a higher density than normal water (in this case, similar density to deuterium oxide). At higher expense (due to the greater difficulty in separation of O-17, a less common heavy isotope of oxygen), water is available in which the oxygen is enriched to varying degrees with ¹⁷O. These types of heavy-isotope water are rarely referred to as "heavy water", as they do not contain the deuterium which gives D₂O its characteristically different nuclear and biological properties. Heavy-oxygen waters with normal hydrogen, for example, would not be expected to show any toxicity whatsoever (see discussion of toxicity below).

Physical properties (with comparison to light water)

^{[citation needed]}

No physical properties are listed for "pure" semi-heavy water, because it cannot be isolated in bulk quantities. In the liquid state, a few water molecules are always in an ionised state, which means the hydrogen atoms can exchange among different oxygen atoms. A sample of hypothetical "pure" semi-heavy water would rapidly transform into a dynamic mixture of 25% light water, 25% heavy water, and 50% semi-heavy water.

Physical properties obvious by inspection: Heavy water is 10.6% denser than ordinary water, a difference which is difficult to notice in a sample of it (although it looks like water, it reportedly tastes slightly sweet^[3]). One of the few ways to demonstrate heavy water's physically different properties without equipment, is to freeze a sample and drop it into normal water. Ice made from heavy water sinks in normal water. If the normal water is ice-cold this phenomenon may be observed long enough for a good demonstration, since heavy-water ice has a slightly higher melting temperature (3.8 °C) than normal ice, and thus holds up very well in ice-cold normal water. ^[4]

History

Harold Urey discovered the isotope deuterium in 1931 and was later able to concentrate it in water.^[5] Urey's mentor Gilbert Newton Lewis isolated the first sample of pure heavy water by electrolysis in 1933. George de Hevesy and Hoffer used heavy water in 1934 in one of the first biological tracer experiments, to estimate the rate of turnover of water in the human body. The history of large-quantity production and use of heavy water in early nuclear experiments is given below.^[6]

Effect on biological systems

Heavy isotopes of chemical elements have slightly different chemical behaviors, but for most elements the differences in chemical behavior between isotopes are far too small to use, or even detect. For hydrogen, however, this is not true. The larger chemical isotope-effects seen with deuterium and tritium manifest because bond energies in chemistry are determined in quantum mechanics by equations in which the quantity of reduced mass of the nucleus and electrons appears. This quantity is altered in heavy-hydrogen compounds (of which deuterium oxide is the most common and familiar) more than for heavy-isotope substitution in other chemical elements. This isotope effect of heavy hydrogen is magnified further in biological systems, which are very sensitive to small changes in the solvent properties of water.

Heavy water is the only known chemical substance that affects the period of circadian oscillations, consistently increasing them. The effect is seen in unicellular organisms, green plants, isopods, insects, birds, mice, and hamsters. The mechanism is unknown.^[7]

To perform their tasks, enzymes rely on their finely tuned networks of hydrogen bonds, both in the active center with their substrates, and outside the active center, to stabilize their tertiary structures. As a hydrogen bond with deuterium is slightly stronger^{[citation needed]} than one involving ordinary hydrogen, in a highly deuterated environment, some normal reactions in cells are disrupted.

Particularly hard-hit by heavy water are the delicate assemblies of mitotic spindle formation necessary for cell division in eukaryotes. Plants stop growing and seeds do not germinate when given only heavy water, because heavy water stops eukaryotic cell division.

It has been proposed that low doses of heavy water can slow the aging process by helping the body resist oxidative damage via the isotope effect.^[8] A team at the Institute for the Biology of Ageing, located in Moscow, conducted an experiment to determine the effect of heavy water on longevity using fruit flies and found that while large amounts were deadly, smaller quantities increased lifespans by up to 30%.^[9]

Effect on animals

Experiments in mice, rats, and dogs^[10] have shown that a degree of 25% deuteration causes (sometimes irreversible) sterility, because neither gametes nor zygotes can develop. High concentrations of heavy water (90%) rapidly kill fish, tadpoles, flatworms, and Drosophila. Mammals, such as rats, given heavy water to drink die after a week, at a time when their body water approaches about 50% deuteration. The mode of death appears to be the same as that in cytotoxic poisoning (such as chemotherapy) or in acute radiation syndrome (though deuterium is not radioactive), and is due to deuterium's action in generally inhibiting cell division. It is more toxic to malignant cells than normal cells but the concentrations needed are too high for regular use.^[10] As in chemotherapy, deuterium-poisoned mammals die of a failure of bone marrow (bleeding and infection) and intestinal-barrier functions (diarrhea and fluid loss).

Notwithstanding the problems of plants and animals in living with too much deuterium, prokaryotic organisms such as bacteria, which do not have the mitotic problems induced by deuterium, may be grown and propagated in fully deuterated conditions, resulting in replacement of all hydrogen atoms in the bacterial proteins and DNA with the deuterium isotope.^[10] Full replacement with heavy atom isotopes can be accomplished in higher organisms with other non-radioactive heavy isotopes (such as carbon-13, nitrogen-15, and oxygen-18), but this cannot be done for the stable heavy isotope of hydrogen.

Deuterium oxide is used to enhance boron neutron capture therapy, but this effect does not rely on the biological effects of deuterium per se, but instead on deuterium's ability to moderate (slow) neutrons without capturing them. ^[10]

Toxicity in humans

Because it would take a very large amount of heavy water to replace 25% to 50% of a human being's body water (which in turn is 70% of body weight) with heavy water, accidental or intentional poisoning with heavy water is unlikely to the point of practical disregard. For a poisoning, large amounts of heavy water would need to be ingested without significant normal water intake for many days to produce any noticeable toxic effects.

Oral doses of heavy water in the multi-gram range, along with heavy oxygen ¹⁸O, are routinely used in human metabolic experiments. See doubly-labeled water testing. Since 1 in every 6400 hydrogen atoms is deuterium, a 50 kg human containing 32 kg of body water would normally contain enough deuterium (about 1.1 gram) to make 5.5 grams of pure heavy water, so roughly this dose is required to double the amount of deuterium in the body.

The US issued patent U.S. Patent 5,223,269 for use of heavy water to treat hypertension (high blood pressure). A loss of blood pressure may partially explain the reported incidents of dizziness upon ingestion.

Confused report of a "heavy water" contamination incident

In 1990, a disgruntled employee at the Point Lepreau Nuclear Generating Station in Canada obtained a sample (estimated as about a "half cup") of heavy water from the primary heat transport loop of the nuclear reactor, and loaded it into the employee water cooler. Eight employees drank some of the contaminated water. The incident was discovered when employees began leaving bioassay urine samples with elevated tritium levels. The quantity of heavy water involved was far below levels that could induce heavy water toxicity, but several employees received elevated radiation doses from tritium and neutron-activated chemicals in the water.^[11] This was not an incident of heavy water poisoning, but rather radiation poisoning from other isotopes in the heavy water. Some news services were not careful to distinguish these points, and some of the public were left with the impression that heavy water is normally radioactive and more severely toxic than it is. Even if pure heavy water had been used in the water cooler indefinitely, it is not likely the incident would have been detected or caused harm, since no employees would be expected to get as much as 25% of their daily drinking water from such a source.^[12]

Production

On Earth, semiheavy water, HDO, occurs naturally in regular water at a proportion of about 1 molecule in 3200. This means that 1 in 6400 hydrogen atoms is deuterium, which is 1 part in 3200 by weight (hydrogen weight). The HDO may be separated from regular water by distillation or electrolysis and also by various chemical exchange processes, all of which exploit a kinetic isotope effect. (For more information about the isotopic distribution of deuterium in water, see Vienna Standard Mean Ocean Water.)

The difference in mass between the two hydrogen isotopes translates into a difference in the zero-point energy and thus into a slight difference in the speed at which the reaction proceeds. Once HDO becomes a significant fraction of the water, heavy water will become more prevalent as water molecules trade hydrogen atoms very frequently. To produce pure heavy water by distillation or electrolysis requires a large cascade of stills or electrolysis chambers, and consumes large amounts of power, so the chemical methods are generally preferred. The most important chemical method is the Girdler sulfide process.

An alternative process^[13], patented by Graham M. Keyser, uses lasers to selectively dissociate deuterated hydrofluorocarbons to form deuterium fluoride, which can then be separated by physical means. Although the energy consumption for this process is much less than for the Girdler sulfide process, this method is currently uneconomical due to the expense of procuring the necessary hydrofluorocarbons.

United States

In 1953, the United States began using heavy water in plutonium production reactors at the Savannah River Site. The first of the five heavy water reactors came online in 1953, and the last was placed in cold shutdown in 1996. The SRS reactors were heavy water reactors so that they could produce both plutonium and tritium for the US nuclear weapons program.

The U.S. developed the Girdler sulfide chemical exchange production process which was first demonstrated on a large scale at the Dana, Indiana plant in 1945 and at the Savannah River Plant, South Carolina in 1952. The SRP was operated by DuPont for the USDOE until 1 April 1989 at which time the operation was taken over by Westinghouse.

Norway

In 1934, Norsk Hydro built the first commercial heavy water plant at Vemork, Tinn, with a capacity of 12 tonnes per year^[14]. From 1940 and throughout World War II, the plant was under German control and the allies decided to destroy the plant and its heavy water to inhibit German development of nuclear weapons. In late 1942, a planned raid by British airborne troops failed, both gliders crashing. The raiders were killed in the crash or subsequently executed by the Germans. In the night of 27 February 1943 Operation Gunnerside succeeded. Norwegian commandos and local resistance managed to demolish small but key parts of the electrolytic cells, dumping the accumulated heavy water down the factory drains. Had the German nuclear program followed similar lines of research as the U.S. Manhattan Project, such heavy water would have been crucial to obtaining plutonium from a nuclear reactor. The Norsk Hydro operation is one of the great commando sabotage operations of the war.

On 16 November 1943, the allied air forces dropped more than 400 bombs on the site. The allied air raid prompted the Nazi government to move all available heavy water to Germany for safekeeping. On 20 February 1944, a Norwegian partisan sank the ferry M/F Hydro carrying the heavy water across Lake Tinn, at the cost of 14 Norwegian civilians' lives, and most of the heavy water was presumably lost. A few of the barrels were only half full, and therefore could float, and may have been salvaged and transported to Germany. (These events were dramatized in the 1965 movie, The Heroes of Telemark.)

Recent investigation of production records at Norsk Hydro and analysis of an intact barrel that was salvaged in 2004 revealed that although the barrels in this shipment contained water of pH 14 — indicative of the alkaline electrolytic refinement process — they did not contain high concentrations of D₂O.^[15] Despite the apparent size of shipment, the total quantity of pure heavy water was quite small, most barrels only containing between 1/2–1% pure heavy water. The Germans would have needed a total of about 5 tons of heavy water to get a nuclear reactor running. The manifest clearly indicated that there was only half a ton of heavy water being transported to Germany. The Hydro was carrying far too little heavy water for even one reactor, let alone the 10 or more tons needed to make enough plutonium for a nuclear weapon.^[15]

Canada

As part of its contribution to the Manhattan Project, Canada built and operated a 6 tonnes per year electrolytic heavy water plant at Trail, BC, which started operation in 1943.

The Atomic Energy of Canada Limited (AECL) design of power reactor requires large quantities of heavy water to act as a neutron moderator and coolant. AECL ordered two heavy water plants which were built and operated in Atlantic Canada at Glace Bay (by Deuterium of Canada Limited) and Port Hawkesbury, Nova Scotia (by General Electric Canada). These plants proved to have significant design, construction and production problems and so AECL built the Bruce Heavy Water Plant (map location), which it later sold to Ontario Hydro, to ensure a reliable supply of heavy water for future power plants. The two Nova Scotia plants were shut down in 1985 when their production proved to be unnecessary.

The Bruce Heavy Water Plant in Ontario was the world's largest heavy water production plant with a capacity of 700 tonnes per year. It used the Girdler sulfide process to produce heavy water, and required 340,000 tonnes of feed water to produce one tonne of heavy water. It was part of a complex that included 8 CANDU reactors which provided heat and power for the heavy water plant. The site was located at Douglas Point in Bruce County on Lake Huron where it had access to the waters of the Great Lakes.

The Bruce plant was commissioned in 1979 to provide heavy water for a large increase in Ontario's nuclear power generation. The plants proved to be significantly more efficient than planned and only three of the planned four units were eventually commissioned. In addition, the nuclear power programme was slowed down and effectively stopped due to a perceived oversupply of electricity, later shown to be temporary, in 1993. Improved efficiency in the use and recycling of heavy water plus the over-production at Bruce left Canada with enough heavy water for its anticipated future needs. Also, the Girdler process involves large amounts of hydrogen sulfide, raising environmental concerns if there should be a release. The Bruce heavy water plant was shut down in 1997, after which the plant was gradually dismantled and the site cleared.

Atomic Energy of Canada Limited (AECL) is currently researching other more efficient and environmentally benign processes for creating heavy water. This is essential for the future of the CANDU reactors since heavy water represents about 20% of the capital cost of each reactor.

India

India is the world's second largest producer of heavy water through its Heavy Water Board.

Iran

On 26 August 2006, Iranian President Ahmadinejad inaugurated an expansion of the country's heavy-water plant near Arak. Iran has indicated that the heavy-water production facility will operate in tandem with a 40 MW research reactor that has a scheduled completion date in 2009.^[16]

Pakistan

The 50 MWt, heavy water and natural uranium research reactor at Khushab, in Punjab province, is a central element of Pakistan's program for production of plutonium, deuterium and tritium for advanced compact warheads. Pakistan succeeded in illicitly acquiring a tritium purification and storage plant, and deuterium and tritium precursor materials from two German firms.^[17]

Other countries

Argentina is another declared producer of heavy water, using an ammonia/hydrogen exchange based plant supplied by Switzerland's Sulzer company.

Romania also produces heavy water at the Drobeta Girdler Sulfide plant and is exporting it from time to time.

France operated a small plant during the 1950s and 1960s.

Applications

Nuclear magnetic resonance

Deuterium oxide is used in nuclear magnetic resonance spectroscopy when the solvent of interest is water and the nuclide of interest is hydrogen. This is because the signal from the water solvent would interfere with the signal from the molecule of interest. Deuterium has a different magnetic moment from hydrogen and therefore does not contribute to the NMR signal at the hydrogen resonance frequency.

Organic Chemistry

Deuterium oxide is often used as the source of deuterium for preparing specifically-labelled isotopologs of organic compounds. For example, C-H bonds adjacent to ketonic carbonyl groups can be replaced by C-D bonds, using acid or base catalysis. Trimethylsulfoxonium iodide, made from dimethylsulfoxide and methyl iodide can be recrystallized from deuterium oxide, and then dissociated to regenerate methyl iodide and dimethylsulfoxide, both deuterium labelled. In cases where specific double labelling by deuterium and tritium is contemplated, the researcher needs to be aware that deuterium oxide, depending upon age and origin, can contain some tritium.

Fourier transform spectroscopy

Deuterium oxide is often used instead of water when collecting FTIR spectra of proteins in solution. H₂O creates a strong band that overlaps with the amide I region of proteins. The band from D₂O is shifted away from the amide I region.

Neutron moderator

Heavy water is used in certain types of nuclear reactors where it acts as a neutron moderator to slow down neutrons so that they are more likely to react with the fissile uranium-235 than with uranium-238 which captures neutrons without fissioning. The CANDU reactor uses this design. Light water also acts as a moderator but because light water absorbs more neutrons than heavy water, reactors using light water must use low enriched uranium rather than natural uranium, otherwise criticality is impossible.

Because they do not require uranium enrichment, heavy water reactors are of concern in regards to nuclear proliferation. The breeding and extraction of plutonium can be a relatively rapid and cheap route to building a nuclear weapon, as chemical separation of plutonium from fuel is easier than isotopic separation of U-235 from natural uranium. Among current and past nuclear weapons states, Israel, India, and North Korea first used plutonium from heavy water moderated reactors burning natural uranium, while China, South Africa and Pakistan first built weapons using highly enriched uranium. However, in the U.S., the first experimental atomic reactor (1942), as well as the Manhattan Project Hanford production reactors which produced the plutonium for the Trinity test and Fat Man bombs, all used pure carbon neutron moderators and functioned with neither enriched uranium nor heavy water. Russian and British plutonium production also used graphite-moderated reactors.

There is no evidence that civilian heavy water power reactors, such as the CANDU or Atucha designs, have been used for military production of fissile materials. In states which do not already possess nuclear weapons, the nuclear material at these facilities is under IAEA safeguards to discourage any such diversion.

Due to its potential for use in nuclear weapons programs, the possession or import/export of large industrial quantities of heavy water are subject to government control in several countries. Suppliers of heavy water and heavy water production technology typically apply IAEA (International Atomic Energy Agency) administered safeguards and material accounting to heavy water. (In Australia, the Nuclear Non-Proliferation (Safeguards) Act 1987.) In the U.S. and Canada, non-industrial quantities of heavy water (i.e., in the gram to kg range) are routinely available through chemical supply dealers, and directly commercial companies such as the world's former major producer Ontario Hydro, without special license. Current (2006) cost of a kilogram of 99.98% reactor-purity heavy water, is about $600 to $700. Smaller quantities of reasonable purity (99.9%) may be purchased from chemical supply houses at prices of roughly $1 per gram.

Neutrino detector

The Sudbury Neutrino Observatory (SNO) in Sudbury, Ontario used 1000 tonnes of heavy water on loan from Atomic Energy of Canada Limited. The neutrino detector is 6800 feet underground in a deep mine, in order to shield it from muons produced by cosmic rays. SNO was built to answer the question of whether or not electron-type neutrinos produced by fusion in the Sun (the only type the Sun should be producing directly, according to theory) might be able to turn into other types of neutrinos on the way to Earth. SNO detects the Čerenkov radiation in the water from high-energy electrons produced from electron-type neutrinos as they undergo reactions with neutrons in deuterium, turning them into protons and electrons (only the electrons move fast enough to be detected in this manner). SNO also detects the same radiation from neutrino↔electron scattering events, which again produces high energy electrons. These two reactions are produced only by electron-type neutrinos. The use of deuterium is critical to the SNO function, because all three "flavours" (types) of neutrinos^[18] may be detected in a third type of reaction, neutrino-disintegration, in which a neutrino of any type (electron, muon, or tau) scatters from a deuterium nucleus (deuteron), transferring enough energy to break up the loosely-bound deuteron into a free neutron and proton. This event is detected when the free neutron is absorbed by ³⁵Cl⁻ present from NaCl which has been deliberately dissolved in the heavy water, causing emission of characteristic capture gamma rays. Thus, in this experiment, heavy water not only provides the transparent medium necessary to produce and visualize Čerenkov radiation, but it also provides deuterium to detect exotic mu type (μ) and tau (τ) neutrinos, as well as a non-absorbent moderator medium to preserve free neutrons from this reaction, until they can be absorbed by an easily-detected neutron-activated isotope.

Metabolic rate testing in physiology/biology

Heavy water is employed as part of a mixture with H₂¹⁸O for a common and safe test of mean metabolic rate in humans and animals undergoing their normal activities. This metabolic test is usually called the doubly-labeled water test.

Tritium production

Tritium is an important material in nuclear weapon design for boosted fission weapons and initiators, and also has civilian industrial applications. Some is created in heavy water moderated reactors when deuterium captures a neutron. This reaction has a small cross-section and produces only small amounts of tritium, although enough so that cleaning tritium from the moderator may be desirable after several years to reduce the risk of tritium escape and radiation exposure.

Production of large amounts of tritium in this way would require reactors with very high neutron fluxes, or with a very high proportion of heavy water to nuclear fuel and very low neutron absorption by other reactor material. The tritium would then have to be recovered by isotope separation from a much larger quantity of deuterium, unlike tritium production from lithium-6 (the present method of tritium production), where only chemical separation is needed.

Deuterium's absorption cross section for thermal neutrons is .52 millibarns, while oxygen-16's is .19 millibarns and oxygen-17's is .24 barn. ¹⁷O makes up .038% of natural oxygen, which has an overall absorption cross section of .28 millibarns. Therefore in D₂O with natural oxygen, 21% of neutron captures are on oxygen, a proportion that may rise further as ¹⁷O accumulates from neutron capture on ¹⁶O. Also, ¹⁷O emits an alpha particle on capture, producing radioactive carbon-14.

See also

Water portal

• Norwegian heavy water sabotage
• Cold fusion
• Vienna Standard Mean Ocean Water
• Deuterium

References

External links

• Thermodynamic Properties of liquid heavy water
• Heavy Water Production, Federation of American Scientists
• Heavy Water: A Manufacturer’s Guide for the Hydrogen Century
• Is "heavy water" dangerous? Straight Dope Staff Report. 09-December-2003
• Annotated bibliography for heavy water from the Alsos Digital Library for Nuclear Issues
• Ice is supposed to float, but with a little heavy water, you can make cubes that sink