Branch of chemistry dealing with radioactivity, transmutation and other nuclear processes
Nuclear chemistry is the sub-field of chemistry dealing with radioactivity, nuclear processes, and transformations in the nuclei of atoms, such as nuclear transmutation 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 behavior under conditions of both normal and abnormal operation (such as during an accident). An important area is the behavior of objects and materials after being placed into a nuclear waste storage or disposal site.
It includes the study of the chemical effects resulting from the absorption of radiation within living animals, plants, and other materials. The radiation chemistry controls much of radiation biology as radiation has an effect on living things at the molecular scale. To explain it another way, the radiation alters the biochemicals within an organism, the alteration of the bio-molecules then changes the chemistry which occurs within the organism; this change in chemistry then can lead to a biological outcome. As a result, nuclear chemistry greatly assists the understanding of medical treatments (such as cancer radiotherapy) and has enabled these treatments to improve.
It includes the study of the production and use of radioactive sources for a range of processes. These include radiotherapy in medical applications; the use of radioactive tracers within industry, science and the environment, and the use of radiation to modify materials such as polymers.
It also includes the study and use of nuclear processes in "non-radioactive" areas of human activity. For instance, nuclear magnetic resonance (NMR) spectroscopy is commonly used in synthetic organic chemistry and physical chemistry and for structural analysis in macro-molecular chemistry.
History.
After Wilhelm Röntgen discovered X-rays in 1895, 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 Skłodowska-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. Henri Becquerel had carried a sample of radium in his pocket and as a result he suffered a highly localized 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 treatment.
Ernest Rutherford, working in Canada and England, showed that radioactive 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 conducted the Geiger–Marsden experiment (gold foil 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.
In 1934, Marie Curie's daughter (Irène Joliot-Curie) and son-in-law (Frédéric Joliot-Curie) were the first to create artificial radioactivity: they bombarded boron with alpha particles to make the neutron-poor isotope nitrogen-13; this isotope emitted positrons. In addition, they bombarded aluminium and magnesium with neutrons to make new radioisotopes.
In the early 1920s Otto Hahn created a new line of research. Using the "emanation method", which he had recently developed, and the "emanation ability", he founded what became known as "applied radiochemistry" for the researching of general chemical and physical-chemical questions. In 1936 Cornell University Press published a book in English (and later in Russian) titled "Applied Radiochemistry", which contained the lectures given by Hahn when he was a visiting professor at Cornell University in Ithaca, New York, in 1933. This important publication had a major influence on almost all nuclear chemists and physicists in the United States, the United Kingdom, France, and the Soviet Union during the 1930s and 1940s, laying the foundation for modern nuclear chemistry.
Hahn and Lise Meitner discovered radioactive isotopes of radium, thorium, protactinium and uranium. He also discovered the phenomena of radioactive recoil and nuclear isomerism, and pioneered rubidium–strontium dating. In 1938, Hahn, Lise Meitner and Fritz Strassmann discovered nuclear fission, for which Hahn received the 1944 Nobel Prize for Chemistry. Nuclear fission was the basis for nuclear reactors and nuclear weapons. Hahn is referred to as the father of nuclear chemistry and godfather of nuclear fission.
Main areas.
Radiochemistry is the chemistry of radioactive materials, in which 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.
Radiation chemistry is the study of the chemical effects of radiation on matter; this is very different from 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. Prior to radiation chemistry, it was commonly believed that pure water could not be destroyed.
Initial experiments were focused on understanding the effects of radiation on matter. Using a X-ray generator, studied the biological effects of radiation as it became a common treatment option and diagnostic method. Fricke proposed and subsequently proved that the energy from X - rays were able to convert water into activated water, allowing it to react with dissolved species.
Chemistry for nuclear power.
Radiochemistry, radiation chemistry and nuclear chemical engineering play a very important role for uranium and thorium fuel precursors synthesis, starting from ores of these elements, fuel fabrication, coolant chemistry, fuel reprocessing, radioactive waste treatment and storage, monitoring of radioactive elements release during reactor operation and radioactive geological storage, etc.
Study of nuclear reactions.
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 short-lived 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 sulfate 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.
This is 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' behavior (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 spent fuel pool 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. Without this process, none of this would be true.
Reprocessing.
Law.
In the United States, 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 used civilian reactor fuel in a deep store. This non-reprocessing policy was started in March 1977 because of concerns about nuclear weapons proliferation. President Jimmy Carter issued a Presidential directive which indefinitely suspended the commercial reprocessing and recycling of plutonium in the United States. This directive was likely an attempt by the United States to lead other countries by example, but many other nations continue to reprocess spent nuclear fuels. The Russian government under President Vladimir Putin repealed a law which had banned the import of used nuclear fuel, which makes it possible for Russians to offer a reprocessing service for clients outside Russia (similar to that offered by BNFL).
PUREX chemistry.
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 bond is formed between the metal cation, the nitrates and the tributyl phosphate, and a model compound of a dioxouranium(VI) complex with two nitrate anions and two triethyl phosphate ligands has been characterised by X-ray crystallography.
When the nitric acid concentration is high the extraction into the organic phase is favored, 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 phosphatioloporus.
New methods being considered for future use.
The PUREX process can be modified to make a UREX ("UR"anium "EX"traction) process which could be used to save space inside high level nuclear waste disposal sites, such as Yucca Mountain nuclear waste repository, 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