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Nuclear chemistry is a subfield of chemistry dealing with radioactivity, nuclear processes and nuclear properties. * It is the chemistry of radioactive elements such as the actinides, radium and radon together with the chemistry associated with equipment (such as nuclear reactors) which are designed to perform nuclear processes. This includes the corrosion of surfaces and the behaviour under conditions of both normal and abnormal operation (such as during an accident). An important area is the behaviour of objects and materials after being placed into a waste store or otherwise disposed of.
After the discovery of X-rays by Wilhelm Röntgen, many scientists began to work on ionizing radiation. One of these was Henri Becquerel, who investigated the relationship between phosphorescence and the blackening of photographic plates. When Becquerel (working in France) discovered that, with no external source of energy, the uranium generated rays which could blacken (or fog) the photographic plate, radioactivity was discovered. Marie Curie (working in Paris) and her husband Pierre Curie isolated two new radioactive elements from uranium ore. They used radiometric methods to identify which stream the radioactivity was in after each chemical separation; they separated the uranium ore into each of the different chemical elements that were known at the time, and measured the radioactivity of each fraction. They then attempted to separate these radioactive fractions further, to isolate a smaller fraction with a higher specific activity (radioactivity divided by mass). In this way, they isolated polonium and radium. It was noticed in about 1901 that high doses of radiation could cause an injury in humans, Becquerel had carried a sample of radium in his pocket and as a result he suffered a high localised dose which resulted in a radiation burn this injury resulted in the biological properties of radiation being investigated, which in time resulted in the development of medical treatments. Marie Curie's daughter (Irène Joliot-Curie) and her husband were the first to 'create' radioactivity: they bombarded boron with alpha particles to make a proton-rich isotope of nitrogen; this isotope emitted positrons. In addition, they bombarded aluminium and magnesium with neutrons to make new radioisotopes. Ernest Rutherford, working in Canada and England, showed that radioactivity decay can be described by a simple equation (a linear first degree derivative equation, now called first order kinetics), implying that a given radioactive substance has a characteristic "half life" (the time taken for the amount of radioactivity present in a source to diminish by half). He also coined the terms alpha, beta and gamma rays, he converted nitrogen into oxygen, and most importantly he supervised the students who did the Geiger-Marsden experiment (gold leaf experiment) which showed that the 'plum pudding model' of the atom was wrong. In the plum pudding model, proposed by J. J. Thomson in 1904, the atom is composed of electrons surrounded by a 'cloud' of positive charge to balance the electrons' negative charge. To Rutherford, the gold foil experiment implied that the positive charge was confined to a very small nucleus leading first to the Rutherford model, and eventually to the Bohr model of the atom, where the positive nucleus is surrounded by the negative electrons.
Radiochemistry is the chemistry of radioactive materials, where radioactive isotopes of elements are used to study the properties and chemical reactions of non-radioactive isotopes (often within radiochemistry the absence of radioactivity leads to a substance being described as being inactive as the isotopes are stable).
For further details please see the page on radiochemistry.
Radiation chemistry is the study of the chemical effects of radiation on matter; this is very different to radiochemistry as no radioactivity needs to be present in the material which is being chemically changed by the radiation. An example is the conversion of water into hydrogen gas and hydrogen peroxide.
Study of nuclear reactions
see also nuclear physics and nuclear reactions for further details.
A combination of radiochemistry and radiation chemistry is used to study nuclear reactions such as fission and fusion. Some early evidence for nuclear fission was the formation of a shortlived radioisotope of barium which was isolated from neutron irradiated uranium (139Ba, with a half-life of 83 minutes and 140Ba, with a half-life of 12.8 days, are major fission products of uranium). At the time, it was thought that this was a new radium isotope, as it was then standard radiochemical practice to use a barium sulphate carrier precipitate to assist in the isolation of radium.. More recently, a combination of radiochemical methods and nuclear physics has been used to try to make new 'superheavy' elements; it is thought that islands of relative stability exist where the nuclides have half-lives of years, thus enabling weighable amounts of the new elements to be isolated. For more details of the original discovery of nuclear fission see the work of Otto Hahn.
The nuclear fuel cycle
The chemistry associated with any part of the nuclear fuel cycle, including nuclear reprocessing. The fuel cycle includes all the operations involved in producing fuel, from mining, ore processing and enrichment to fuel production (Front end of the cycle). It also includes the 'in-pile' behaviour (use of the fuel in a reactor) before the back end of the cycle. The back end includes the management of the used nuclear fuel in either a cooling pond or dry storage, before it is disposed of into an underground waste store or reprocessed.
Normal and abnormal conditions
The nuclear chemistry associated with the nuclear fuel cycle can be divided into two main areas, one area is concerned with operation under the intended conditions while the other area is concerned with maloperation conditions where some alteration from the normal operating conditions has occurred or (more rarely) an accident is occurring.
In the USA it is normal to use fuel once in a power reactor before placing it in a waste store. The long term plan is currently to place the civil used power reactor fuel in a deep store. This policy of not reprocessing was started in March 1977 for nuclear weapons proliferation reasons. The President Jimmy Carter issued a Presidential directive which indefinitely suspended the commercial reprocessing and recycling of plutonium in the USA. This Presidential directive is likely to have been an attempt by the USA to lead other countries by example, but many other nations continue to reprocess spent nuclear fuels. It is noteworthy that the government under Putin (President of Russia) repealed a law which had banned the import of used nuclear fuel into Russia, this change in Russian law now permits the Russians to offer a reprocessing service for clients outside Russia (In a similar way to that offered by BNFL).
The current method of choice is to use the PUREX liquid-liquid extraction process which uses a tributyl phosphate/hydrocarbon mixture to extract both uranium and plutonium from nitric acid. This extraction is of the nitrate salts and is classed as being of a solvation mechanism. For example the extraction of plutonium by an extraction agent (S) in a nitrate medium occurs by the following reaction.
Pu4+aq + 4NO3-aq + 2Sorganic --> [Pu(NO3)4S2]organic
A complex is formed between the metal cation, the nitrates and the tributyl phosphate, and a model compound of a dioxouranium(VI) complex with two nitrates and two triethyl phosphates has been characterised by X-ray crystallography.
When the nitric acid concentration is high the extraction into the organic phase is favoured, and when the nitric acid concentration is low the extraction is reversed (the organic phase is stripped of the metal). It is normal to dissolve the used fuel in nitric acid, after the removal of the insoluble matter the uranium and plutonium are extracted from the highly active liquor. It is normal to then back extract the loaded organic phase to create a medium active liquor which contains mostly uranium and plutonium with only small traces of fission products. This medium active aqueous mixture is then extracted again by tributyl phosphate/hydrocarbon to form a new organic phase, the metal bearing organic phase is then stripped of the metals to form an aqueous mixture of only uranium and plutonium. The two stages of extraction are used to improve the purity of the actinide product, the organic phase used for the first extraction will suffer a far greater dose of radiation. The radiation can degrade the tributyl phosphate into dibutyl hydrogen phosphate. The dibutyl hydrogen phosphate can act as an extraction agent for both the actinides and other metals such as ruthenium. The dibutyl hydrogen phosphate can make the system behave in a more complex manner as it tends to extract metals by an ion exchange mechanism (extraction favoured by low acid concentration), to reduce the effect of the dibutyl hydrogen phosphate it is common for the used organic phase to be washed with sodium carbonate solution to remove the acidic degradation products of the tributyl phosphate.
New methods being considered for future use
The PUREX process can be modified to make a UREX (URanium EXtraction) process which could be used to save space inside high level nuclear waste disposal sites, such as Yucca Mountain, by removing the uranium which makes up the vast majority of the mass and volume of used fuel and recycling it as reprocessed uranium.
The UREX process is a PUREX process which has been modified to prevent the plutonium being extracted. This can be done by adding a plutonium reductant before the first metal extraction step. In the UREX process, ~99.9% of the Uranium and >95% of Technetium are separated from each other and the other fission products and actinides. The key is the addition of acetohydroxamic acid (AHA) to the extraction and scrub sections of the process. The addition of AHA greatly diminishes the extractability of Plutonium and Neptunium, providing greater proliferation resistance than with the plutonium extraction stage of the PUREX process.
Adding a second extraction agent, octyl(phenyl)-N, N-dibutyl carbamoylmethyl phosphine oxide(CMPO) in combination with tributylphosphate, (TBP), the PUREX process can be turned into the TRUEX (TRansUranic EXtraction) process this is a process which was invented in the USA by Argonne National Laboratory, and is designed to remove the transuranic metals (Am/Cm) from waste. The idea is that by lowering the alpha activity of the waste, the majority of the waste can then be disposed of with greater ease. In common with PUREX this process operates by a solvation mechanism.
As an alternative to TRUEX, an extraction process using a malondiamide has been devised. The DIAMEX (DIAMideEXtraction) process has the advantage of avoiding the formation of organic waste which contains elements other than Carbon, Hydrogen, Nitrogen, and Oxygen. Such an organic waste can be burned without the formation of acidic gases which could contribute to acid rain. The DIAMEX process is being worked on in Europe by the French CEA. The process is sufficiently mature that an industrial plant could be constructed with the existing knowledge of the process. In common with PUREX this process operates by a solvation mechanism.
Selective ActiNide EXtraction. As part of the management of minor actinides it has been proposed that the lanthanides and trivalent minor actinides should be removed from the PUREX raffinate by a process such as DIAMEX or TRUEX. In order to allow the actinides such as americium to be either reused in industrial sources or used as fuel the lanthanides must be removed. The lanthanides has large neutron cross sections and hence they would poison a neutron driven nuclear reaction. To date the extraction system for the SANEX process has not been defined, but currently several different research groups are working towards a process. For instance the French CEA is working on a bis-triaiznyl pyridine (BTP) based process.
Other systems such as the dithiophosphinic acids are being worked on by some other workers.
This is the UNiversal EXtraction process which was developed in Russia and the Czech Republic, it is a process designed to remove all of the most troublesome (Sr, Cs and minor actinides) radioisotopes from the raffinates left after the extraction of uranium and plutonium from used nuclear fuel.  The chemistry is based upon the interaction of cesium and strontium with poly ethylene oxide (poly ethylene glycol)  and a cobalt carborane anion (known as chlorinated cobalt dicarbollide) . The actinides are extracted by CMPO, and the diluent is a polar aromatic such as nitrobenzene. Other dilents such as meta-nitrobenzotrifluoride and phenyl trifluoromethyl sulfone have been suggested as well.
Absorption of fission products on surfaces
Another important area of nuclear chemistry is the study of how fission products interact with surfaces; this is thought to control the rate of release and migration of fission products both from waste containers under normal conditions and from power reactors under accident conditions. It is interesting to note that, like chromate and molybdate, the 99TcO4 anion can react with steel surfaces to form a corrosion resistant layer. In this way, these metaloxo anions act as anodic corrosion inhibitors. The formation of 99TcO2 on steel surfaces is one effect which will retard the release of 99Tc from nuclear waste drums and nuclear equipment which has been lost before decontamination (eg submarine reactors lost at sea). This 99TcO2 layer renders the steel surface passive, inhibiting the anodic corrosion reaction. The radioactive nature of technetium makes this corrosion protection impractical in almost all situations. It has also been shown that 99TcO4 anions react to form a layer on the surface of activated carbon (charcoal) or aluminium.. A short review of the biochemical properties of a series of key long lived radioisotopes can be read on line.
It is important to note that 99Tc in nuclear waste may exist in chemical forms other than the 99TcO4 anion, these other forms have different chemical properties.
Some methods first developed within nuclear chemistry and physics have become so widely used within chemistry and other physical sciences that they may be best thought of as separate from normal nuclear chemistry. For example, the isotope effect is used so extensively to investigate chemical mechanisms and the use of cosmogenic isotopes and long-lived unstable isotopes in geology that it is best to consider much of isotopic chemistry as separate from nuclear chemistry.
Kinetics (use within mechanistic chemistry)
The mechanisms of chemical reactions can be investigated by observing how the kinetics of a reaction are changed by making an isotopic modification of a substrate. This is now a standard method in organic chemistry. Briefly, replacing normal hydrogens (protons) by deuterium within a chemical compound causes the rate of molecular vibration (C-H, N-H and O-H bonds show this) to decrease. This then can lead to a decrease in the reaction rate if the rate-determining step involves breaking a bond between hydrogen and another atom. Thus, if the reaction changes in rate when protons are replaced by deuteriums, it is reasonable to assume that the breaking of the bond to hydrogen is part of the step which determines the rate.
Uses within geology, biology and forensic science
Cosmogenic isotopes are formed by the interaction of cosmic rays with the nucleus of an atom. These can be used for dating purposes and for use as natural tracers. In addition, by careful measurement of some ratios of stable isotopes it is possible to obtain new insights into the origin of bullets, ages of ice samples, ages of rocks, and the diet of a person can be identified from a hair or other tissue sample. (See Isotope geochemistry and Isotopic signature for further details).
Within living things, isotopic labels (both radioactive and nonradioactive) can be used to probe how the complex web of reactions which makes up the metabolism of an organism converts one substance to another. For instance a green plant uses light energy to convert water and carbon dioxide into glucose by photosynthesis. If the oxygen in the water is labeled, then the label appears in the oxygen gas formed by the plant and not in the glucose formed in the chloroplasts within the plant cells.
For biochemical and physiological experiments and medical methods, a number of specific isotopes have important applications.
By organic synthesis it is possible to create a complex molecule with a radioactive label that can be confined to a small area of the molecule. For short-lived isotopes such as 11C, very rapid synthetic methods have been developed to permit the rapid addition of the radioactive isotope to the molecule. For instance a palladium catalysed carbonylation reaction in a microfluidic device has been used to rapidly form amides and it might be possible to use this method to form radioactive imaging agents for PET imaging.
Nuclear magnetic resonance (NMR)
NMR spectroscopy uses the net spin of nuclei in a substances upon energy absorption to identify molecules. This has now become a standard spectroscopic tool within synthetic chemistry. One major use of NMR is to determine the bond connectivity within an organic molecule.
NMR imaging also uses the net spin of nuclei (commonly protons) for imaging. This is widely used for diagnostic purposes in medicine, and can provide detailed images of the inside of a person without inflicting any radiation upon them. In a medical setting, NMR is often known simply as "magnetic resonance" imaging, as the word 'nuclear' has negative connotations for many people.
|This article is licensed under the GNU Free Documentation License. It uses material from the Wikipedia article "Nuclear_chemistry". A list of authors is available in Wikipedia.|