![Alpha Decay](https://upload.wikimedia.org/wikipedia/commons/7/79/Alpha_Decay.svg)
Nuclear chemistry is the sub-field of
chemistry
Chemistry is the science, scientific study of the properties and behavior of matter. It is a natural science that covers the Chemical element, elements that make up matter to the chemical compound, compounds made of atoms, molecules and ions ...
dealing with
radioactivity, nuclear processes, and transformations in the nuclei of atoms, such as
nuclear transmutation
Nuclear transmutation is the conversion of one chemical element or an isotope into another chemical element. Nuclear transmutation occurs in any process where the number of protons or neutrons in the nucleus of an atom is changed.
A transmutatio ...
and nuclear properties.
It is the chemistry of
radioactive
Radioactive decay (also known as nuclear decay, radioactivity, radioactive disintegration, or nuclear disintegration) is the process by which an unstable atomic nucleus loses energy by radiation. A material containing unstable nuclei is consid ...
elements such as the
actinides
The actinide () or actinoid () series encompasses the 15 metallic chemical elements with atomic numbers from 89 to 103, actinium through lawrencium. The actinide series derives its name from the first element in the series, actinium. The inform ...
,
radium
Radium is a chemical element with the symbol Ra and atomic number 88. It is the sixth element in group 2 of the periodic table, also known as the alkaline earth metals. Pure radium is silvery-white, but it readily reacts with nitrogen (rather t ...
and
radon
Radon is a chemical element with the symbol Rn and atomic number 86. It is a radioactive, colourless, odourless, tasteless noble gas. It occurs naturally in minute quantities as an intermediate step in the normal radioactive decay chains through ...
together with the chemistry associated with equipment (such as
nuclear reactor
A nuclear reactor is a device used to initiate and control a fission nuclear chain reaction or nuclear fusion reactions. Nuclear reactors are used at nuclear power plants for electricity generation and in nuclear marine propulsion. Heat from nu ...
s) which are designed to perform nuclear processes. This includes the
corrosion
Corrosion is a natural process that converts a refined metal into a more chemically stable oxide. It is the gradual deterioration of materials (usually a metal) by chemical or electrochemical reaction with their environment. Corrosion engine ...
of surfaces and the behavior under conditions of both normal and abnormal operation (such as during an
accident
An accident is an unintended, normally unwanted event that was not directly caused by humans. The term ''accident'' implies that nobody should be blamed, but the event may have been caused by unrecognized or unaddressed risks. Most researcher ...
). An important area is the behavior of objects and materials after being placed into a
nuclear waste
Radioactive waste is a type of hazardous waste that contains radioactive material. Radioactive waste is a result of many activities, including nuclear medicine, nuclear research, nuclear power generation, rare-earth mining, and nuclear weapons r ...
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 Radiation chemistry is a subdivision of nuclear chemistry which 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 ...
controls much of
radiation biology
Radiobiology (also known as radiation biology, and uncommonly as actinobiology) is a field of clinical and basic medical sciences that involves the study of the action of ionizing radiation on living things, especially health effects of radiation. ...
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
Chemistry is the science, scientific study of the properties and behavior of matter. It is a natural science that covers the Chemical element, elements that make up matter to the chemical compound, compounds made of atoms, molecules and ions ...
then can lead to a biological outcome. As a result, nuclear chemistry greatly assists the understanding of medical treatments (such as
cancer
Cancer is a group of diseases involving abnormal cell growth with the potential to invade or spread to other parts of the body. These contrast with benign tumors, which do not spread. Possible signs and symptoms include a lump, abnormal b ...
radiotherapy
Radiation therapy or radiotherapy, often abbreviated RT, RTx, or XRT, is a therapy using ionizing radiation, generally provided as part of cancer treatment to control or kill malignant cells and normally delivered by a linear accelerator. Radia ...
) 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
Radiation therapy or radiotherapy, often abbreviated RT, RTx, or XRT, is a therapy using ionizing radiation, generally provided as part of cancer treatment to control or kill malignant cells and normally delivered by a linear accelerator. Radia ...
in medical applications; the use of
radioactive tracer
A radioactive tracer, radiotracer, or radioactive label is a chemical compound in which one or more atoms have been replaced by a radionuclide so by virtue of its radioactive decay it can be used to explore the mechanism of chemical reactions by ...
s within industry, science and the environment, and the use of radiation to modify materials such as
polymer
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic a ...
s.
It also includes the study and use of nuclear processes in ''non-radioactive'' areas of human activity. For instance,
nuclear magnetic resonance
Nuclear magnetic resonance (NMR) is a physical phenomenon in which nuclei in a strong constant magnetic field are perturbed by a weak oscillating magnetic field (in the near field) and respond by producing an electromagnetic signal with a ...
(NMR) spectroscopy is commonly used in synthetic
organic chemistry
Organic chemistry is a subdiscipline within chemistry involving the scientific study of the structure, properties, and reactions of organic compounds and organic materials, i.e., matter in its various forms that contain carbon atoms.Clayden, J.; ...
and
physical chemistry
Physical chemistry is the study of macroscopic and microscopic phenomena in chemical systems in terms of the principles, practices, and concepts of physics such as motion, energy, force, time, thermodynamics, quantum chemistry, statistical mecha ...
and for structural analysis in
macro-molecular chemistry.
History
After
Wilhelm Röntgen
Wilhelm Conrad Röntgen (; ; 27 March 184510 February 1923) was a German mechanical engineer and physicist, who, on 8 November 1895, produced and detected electromagnetic radiation in a wavelength range known as X-rays or Röntgen rays, an achiev ...
discovered
X-ray
An X-ray, or, much less commonly, X-radiation, is a penetrating form of high-energy electromagnetic radiation. Most X-rays have a wavelength ranging from 10 picometers to 10 nanometers, corresponding to frequencies in the range 30&nb ...
s in 1882, many scientists began to work on ionizing radiation. One of these was
Henri Becquerel
Antoine Henri Becquerel (; 15 December 1852 – 25 August 1908) was a French engineer, physicist, Nobel laureate, and the first person to discover evidence of radioactivity. For work in this field he, along with Marie Skłodowska-Curie and P ...
, who investigated the relationship between
phosphorescence
Phosphorescence is a type of photoluminescence related to fluorescence. When exposed to light (radiation) of a shorter wavelength, a phosphorescent substance will glow, absorbing the light and reemitting it at a longer wavelength. Unlike fluo ...
and the blackening of
photographic plate
Photographic plates preceded photographic film as a capture medium in photography, and were still used in some communities up until the late 20th century. The light-sensitive emulsion of silver salts was coated on a glass plate, typically thinn ...
s. 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
Pierre Curie ( , ; 15 May 1859 – 19 April 1906) was a French physicist, a pioneer in crystallography, magnetism, piezoelectricity, and radioactivity. In 1903, he received the Nobel Prize in Physics with his wife, Marie Curie, and Henri Becqu ...
isolated two new radioactive elements from uranium ore. They used
radiometric
Radiometry is a set of techniques for measuring electromagnetic radiation, including visible light. Radiometric techniques in optics characterize the distribution of the radiation's power in space, as opposed to photometric techniques, which cha ...
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
Polonium is a chemical element with the symbol Po and atomic number 84. Polonium is a chalcogen. A rare and highly radioactive metal with no stable isotopes, polonium is chemically similar to selenium and tellurium, though its metallic character ...
and
radium
Radium is a chemical element with the symbol Ra and atomic number 88. It is the sixth element in group 2 of the periodic table, also known as the alkaline earth metals. Pure radium is silvery-white, but it readily reacts with nitrogen (rather t ...
. It was noticed in about 1901 that high doses of radiation could cause an injury in humans.
Henri Becquerel
Antoine Henri Becquerel (; 15 December 1852 – 25 August 1908) was a French engineer, physicist, Nobel laureate, and the first person to discover evidence of radioactivity. For work in this field he, along with Marie Skłodowska-Curie and P ...
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
A radiation burn is a damage to the skin or other biological tissue and organs as an effect of radiation. The radiation types of greatest concern are thermal radiation, radio frequency energy, ultraviolet light and ionizing radiation.
The most ...
. This injury resulted in the biological properties of radiation being investigated, which in time resulted in the development of medical treatment.
Ernest Rutherford
Ernest Rutherford, 1st Baron Rutherford of Nelson, (30 August 1871 – 19 October 1937) was a New Zealand physicist who came to be known as the father of nuclear physics.
''Encyclopædia Britannica'' considers him to be the greatest ...
, 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
In chemistry, the rate law or rate equation for a reaction is an equation that links the initial or forward reaction rate with the concentrations or pressures of the reactants and constant parameters (normally rate coefficients and partial reactio ...
), implying that a given radioactive substance has a characteristic "
half-life
Half-life (symbol ) is the time required for a quantity (of substance) to reduce to half of its initial value. The term is commonly used in nuclear physics to describe how quickly unstable atoms undergo radioactive decay or how long stable ato ...
" (the time taken for the amount of radioactivity present in a source to diminish by half). He also coined the terms
alpha
Alpha (uppercase , lowercase ; grc, ἄλφα, ''álpha'', or ell, άλφα, álfa) is the first letter of the Greek alphabet. In the system of Greek numerals, it has a value of one. Alpha is derived from the Phoenician letter aleph , whic ...
,
beta
Beta (, ; uppercase , lowercase , or cursive ; grc, βῆτα, bē̂ta or ell, βήτα, víta) is the second letter of the Greek alphabet. In the system of Greek numerals, it has a value of 2. In Modern Greek, it represents the voiced labiod ...
and
gamma rays
A gamma ray, also known as gamma radiation (symbol γ or \gamma), is a penetrating form of electromagnetic radiation arising from the radioactive decay of atomic nuclei. It consists of the shortest wavelength electromagnetic waves, typically ...
, he converted
nitrogen
Nitrogen is the chemical element with the symbol N and atomic number 7. Nitrogen is a nonmetal and the lightest member of group 15 of the periodic table, often called the pnictogens. It is a common element in the universe, estimated at se ...
into
oxygen
Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements as wel ...
, and most importantly he supervised the students who conducted the
Geiger–Marsden experiment (gold foil experiment) which showed that the '
plum pudding model
The plum pudding model is one of several historical scientific models of the atom. First proposed by J. J. Thomson in 1904 soon after the discovery of the electron, but before the discovery of the atomic nucleus, the model tried to explain two pr ...
' of the
atom
Every atom is composed of a nucleus and one or more electrons bound to the nucleus. The nucleus is made of one or more protons and a number of neutrons. Only the most common variety of hydrogen has no neutrons.
Every solid, liquid, gas, and ...
was wrong. In the plum pudding model, proposed by
J. J. Thomson
Sir Joseph John Thomson (18 December 1856 – 30 August 1940) was a British physicist and Nobel Laureate in Physics, credited with the discovery of the electron, the first subatomic particle to be discovered.
In 1897, Thomson showed that c ...
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
The Rutherford model was devised by the New Zealand-born physicist Ernest Rutherford to describe an atom. Rutherford directed the Geiger–Marsden experiment in 1909, which suggested, upon Rutherford's 1911 analysis, that J. J. Thomson's plum ...
, and eventually to the
Bohr model
In atomic physics, the Bohr model or Rutherford–Bohr model, presented by Niels Bohr and Ernest Rutherford in 1913, is a system consisting of a small, dense nucleus surrounded by orbiting electrons—similar to the structure of the Solar Syste ...
of the atom, where the positive nucleus is surrounded by the negative electrons.
In 1934,
Marie Curie
Marie Salomea Skłodowska–Curie ( , , ; born Maria Salomea Skłodowska, ; 7 November 1867 – 4 July 1934) was a Polish and naturalized-French physicist and chemist who conducted pioneering research on radioactivity. She was the first ...
's daughter (
Irène Joliot-Curie
Irène Joliot-Curie (; ; 12 September 1897 – 17 March 1956) was a French chemist, physicist and politician, the elder daughter of Pierre and Marie Curie, and the wife of Frédéric Joliot-Curie. Jointly with her husband, Joliot-Curie was award ...
) and son-in-law (
Frédéric Joliot-Curie
Jean Frédéric Joliot-Curie (; ; 19 March 1900 – 14 August 1958) was a French physicist and husband of Irène Joliot-Curie, with whom he was jointly awarded the Nobel Prize in Chemistry in 1935 for their discovery of Induced radioactivity. T ...
) were the first to create
artificial radioactivity
Induced radioactivity, also called artificial radioactivity or man-made radioactivity, is the process of using radiation to make a previously stable material radioactive. The husband and wife team of Irène Joliot-Curie and Frédéric Joliot-Curie ...
: they bombarded
boron
Boron is a chemical element with the symbol B and atomic number 5. In its crystalline form it is a brittle, dark, lustrous metalloid; in its amorphous form it is a brown powder. As the lightest element of the ''boron group'' it has th ...
with alpha particles to make the neutron-poor isotope
nitrogen-13
Nitrogen-13 (13N) is a radioisotope of nitrogen used in positron emission tomography (PET). It has a half-life of a little under ten minutes, so it must be made at the PET site. A cyclotron may be used for this purpose.
Nitrogen-13 is used to tag ...
; this isotope emitted
positron
The positron or antielectron is the antiparticle or the antimatter counterpart of the electron. It has an electric charge of +1 '' e'', a spin of 1/2 (the same as the electron), and the same mass as an electron. When a positron collides ...
s. In addition, they bombarded
aluminium
Aluminium (aluminum in American and Canadian English) is a chemical element with the symbol Al and atomic number 13. Aluminium has a density lower than those of other common metals, at approximately one third that of steel. I ...
and
magnesium
Magnesium is a chemical element with the symbol Mg and atomic number 12. It is a shiny gray metal having a low density, low melting point and high chemical reactivity. Like the other alkaline earth metals (group 2 of the periodic ta ...
with
neutrons
The neutron is a subatomic particle, symbol or , which has a neutral (not positive or negative) charge, and a mass slightly greater than that of a proton. Protons and neutrons constitute the nuclei of atoms. Since protons and neutrons behave ...
to make new radioisotopes.
In the early 1920s
Otto Hahn
Otto Hahn (; 8 March 1879 – 28 July 1968) was a German chemist who was a pioneer in the fields of radioactivity and radiochemistry. He is referred to as the father of nuclear chemistry and father of nuclear fission. Hahn and Lise Meitner ...
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
Cornell University is a private statutory land-grant research university based in Ithaca, New York. It is a member of the Ivy League. Founded in 1865 by Ezra Cornell and Andrew Dickson White, Cornell was founded with the intention to teach an ...
in
Ithaca, New York
Ithaca is a city in the Finger Lakes region of New York, United States. Situated on the southern shore of Cayuga Lake, Ithaca is the seat of Tompkins County and the largest community in the Ithaca metropolitan statistical area. It is named a ...
, 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 nucelar chemistry.
Hahn and
Lise Meitner
Elise Meitner ( , ; 7 November 1878 – 27 October 1968) was an Austrian-Swedish physicist who was one of those responsible for the discovery of the element protactinium and nuclear fission. While working at the Kaiser Wilhelm Institute on rad ...
discovered radioactive
isotopes of radium
Radium (88Ra) has no stable or nearly stable isotopes, and thus a standard atomic weight cannot be given. The longest lived, and most common, isotope of radium is 226Ra with a half-life of . 226Ra occurs in the decay chain of 238U (often referre ...
,
thorium
Thorium is a weakly radioactive metallic chemical element with the symbol Th and atomic number 90. Thorium is silvery and tarnishes black when it is exposed to air, forming thorium dioxide; it is moderately soft and malleable and has a high me ...
,
protactinium
Protactinium (formerly protoactinium) is a chemical element with the symbol Pa and atomic number 91. It is a dense, silvery-gray actinide metal which readily reacts with oxygen, water vapor and inorganic acids. It forms various chemical compounds ...
and
uranium
Uranium is a chemical element with the symbol U and atomic number 92. It is a silvery-grey metal in the actinide series of the periodic table. A uranium atom has 92 protons and 92 electrons, of which 6 are valence electrons. Uranium is weak ...
. He also discovered the phenomena of radioactive recoil and
nuclear isomerism
A nuclear isomer is a metastable state of an atomic nucleus, in which one or more nucleons (protons or neutrons) occupy excited state, higher energy levels than in the ground state of the same nucleus. "Metastable" describes nuclei whose excited ...
, and pioneered
rubidium–strontium dating
The rubidium-strontium dating method is a radiometric dating technique, used by scientists to determine the age of rocks and minerals from their content of specific isotopes of rubidium (87Rb) and strontium (87Sr, 86Sr). One of the two naturally o ...
. In 1938, Hahn, Lise Meitner and
Fritz Strassmann
Friedrich Wilhelm Strassmann (; 22 February 1902 – 22 April 1980) was a German chemist who, with Otto Hahn in December 1938, identified the element barium as a product of the bombardment of uranium with neutrons. Their observation was the key ...
discovered nuclear fission, for which Hahn received the 1944
Nobel Prize for Chemistry
)
, image = Nobel Prize.png
, alt = A golden medallion with an embossed image of a bearded man facing left in profile. To the left of the man is the text "ALFR•" then "NOBEL", and on the right, the text (smaller) "NAT•" then "M ...
.
Nuclear fission
Nuclear fission is a reaction in which the nucleus of an atom splits into two or more smaller nuclei. The fission process often produces gamma photons, and releases a very large amount of energy even by the energetic standards of radio ...
was the basis for
nuclear reactor
A nuclear reactor is a device used to initiate and control a fission nuclear chain reaction or nuclear fusion reactions. Nuclear reactors are used at nuclear power plants for electricity generation and in nuclear marine propulsion. Heat from nu ...
s and
nuclear weapon
A nuclear weapon is an explosive device that derives its destructive force from nuclear reactions, either fission (fission bomb) or a combination of fission and fusion reactions ( thermonuclear bomb), producing a nuclear explosion. Both bom ...
s. Hahn is referred to as the father of nuclear chemistry and godfather of
nuclear fission
Nuclear fission is a reaction in which the nucleus of an atom splits into two or more smaller nuclei. The fission process often produces gamma photons, and releases a very large amount of energy even by the energetic standards of radio ...
.
Main areas
Radiochemistry
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 ...
is the chemistry of radioactive materials, in which radioactive
isotope
Isotopes are two or more types of atoms that have the same atomic number (number of protons in their nuclei) and position in the periodic table (and hence belong to the same chemical element), and that differ in nucleon numbers (mass numbers) ...
s of elements are used to study the properties and
chemical reaction
A chemical reaction is a process that leads to the IUPAC nomenclature for organic transformations, chemical transformation of one set of chemical substances to another. Classically, chemical reactions encompass changes that only involve the pos ...
s 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
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 ...
.
Radiation chemistry
Radiation chemistry Radiation chemistry is a subdivision of nuclear chemistry which 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 ...
is the study of the chemical effects of radiation on the matter; this is very different from
radiochemistry
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 ...
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
Hydrogen is the chemical element with the symbol H and atomic number 1. Hydrogen is the lightest element. At standard conditions hydrogen is a gas of diatomic molecules having the formula . It is colorless, odorless, tasteless, non-toxic, an ...
gas and
hydrogen peroxide
Hydrogen peroxide is a chemical compound with the formula . In its pure form, it is a very pale blue liquid that is slightly more viscous than water. It is used as an oxidizer, bleaching agent, and antiseptic, usually as a dilute solution (3% ...
. 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,
Hugo Fricke
Hugo Fricke (August 15, 1892, in Aarhus, Denmark – April 5, 1972, in Huntington, New York, US) was a Danish-American physicist who studied the chemical (radiolysis) and biological (radiation biology) effects of X-ray and electron beams and who ...
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
Radioactive waste is a type of hazardous waste that contains radioactive material. Radioactive waste is a result of many activities, including nuclear medicine, nuclear research, nuclear power generation, rare-earth mining, and nuclear weapons r ...
treatment and storage, monitoring of radioactive elements release during reactor operation and radioactive geological storage, etc.
Study of nuclear reactions
A combination of
radiochemistry
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 ...
and
radiation chemistry Radiation chemistry is a subdivision of nuclear chemistry which 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 ...
is used to study nuclear reactions such as
fission and
fusion
Fusion, or synthesis, is the process of combining two or more distinct entities into a new whole.
Fusion may also refer to:
Science and technology Physics
*Nuclear fusion, multiple atomic nuclei combining to form one or more different atomic nucl ...
. Some early evidence for nuclear fission was the formation of a short-lived radioisotope of
barium
Barium is a chemical element with the symbol Ba and atomic number 56. It is the fifth element in group 2 and is a soft, silvery alkaline earth metal. Because of its high chemical reactivity, barium is never found in nature as a free element.
Th ...
which was isolated from
neutron
The neutron is a subatomic particle, symbol or , which has a neutral (not positive or negative) charge, and a mass slightly greater than that of a proton. Protons and neutrons constitute the nuclei of atoms. Since protons and neutrons beh ...
irradiated
uranium
Uranium is a chemical element with the symbol U and atomic number 92. It is a silvery-grey metal in the actinide series of the periodic table. A uranium atom has 92 protons and 92 electrons, of which 6 are valence electrons. Uranium is weak ...
(
139Ba, with a half-life of 83 minutes and
140Ba, with a half-life of 12.8 days, are major
fission product
Nuclear fission products are the atomic fragments left after a large atomic nucleus undergoes nuclear fission. Typically, a large nucleus like that of uranium fissions by splitting into two smaller nuclei, along with a few neutrons, the release ...
s 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
Radium is a chemical element with the symbol Ra and atomic number 88. It is the sixth element in group 2 of the periodic table, also known as the alkaline earth metals. Pure radium is silvery-white, but it readily reacts with nitrogen (rather t ...
. 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
Otto Hahn (; 8 March 1879 – 28 July 1968) was a German chemist who was a pioneer in the fields of radioactivity and radiochemistry. He is referred to as the father of nuclear chemistry and father of nuclear fission. Hahn and Lise Meitner ...
.
The nuclear fuel cycle
This is the chemistry associated with any part of the
nuclear fuel cycle
The nuclear fuel cycle, also called nuclear fuel chain, is the progression of nuclear fuel through a series of differing stages. It consists of steps in the ''front end'', which are the preparation of the fuel, steps in the ''service period'' in w ...
, including
nuclear reprocessing
Nuclear reprocessing is the chemical separation of fission products and actinides from spent nuclear fuel. Originally, reprocessing was used solely to extract plutonium for producing nuclear weapons. With commercialization of nuclear power, the ...
. 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
Spent nuclear fuel, occasionally called used nuclear fuel, is nuclear fuel that has been irradiated in a nuclear reactor (usually at a nuclear power plant). It is no longer useful in sustaining a nuclear reaction in an ordinary thermal reactor an ...
in either a
spent fuel pool
Spent fuel pools (SFP) are storage pools (or "ponds" in the United Kingdom) for spent fuel from nuclear reactors. They are typically 40 or more feet (12 m) deep, with the bottom 14 feet (4.3 m) equipped with storage racks designed to hold f ...
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
Nuclear proliferation is the spread of nuclear weapons, fissionable material, and weapons-applicable nuclear technology and information to nations not recognized as " Nuclear Weapon States" by the Treaty on the Non-Proliferation of Nuclear We ...
. President
Jimmy Carter
James Earl Carter Jr. (born October 1, 1924) is an American politician who served as the 39th president of the United States from 1977 to 1981. A member of the Democratic Party (United States), Democratic Party, he previously served as th ...
issued a
Presidential directive
A presidential directive, or executive action, is a written or oral instruction or declaration issued by the president of the United States, which may draw upon the powers vested in the president by the U.S. Constitution, statutory law, or, in cert ...
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
Vladimir Vladimirovich Putin; (born 7 October 1952) is a Russian politician and former intelligence officer who holds the office of president of Russia. Putin has served continuously as president or prime minister since 1999: as prime min ...
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
British Nuclear Fuels Limited (BNFL) was a nuclear energy and fuels company owned by the UK Government. It was a manufacturer of nuclear fuel (notably MOX), ran reactors, generated and sold electricity, reprocessed and managed spent fuel (mainly ...
).
=PUREX chemistry
=
The current method of choice is to use the
PUREX
PUREX (plutonium uranium reduction extraction) is a chemical method used to purify fuel for nuclear reactors or nuclear weapons. PUREX is the ''de facto'' standard aqueous nuclear reprocessing method for the recovery of uranium and plutonium fr ...
liquid-liquid extraction process which uses a
tributyl phosphate
Tributyl phosphate, known commonly as TBP, is an organophosphorus compound with the chemical formula (CH3CH2CH2CH2O)3PO. This colourless, odorless liquid finds some applications as an extractant and a plasticizer. It is an ester of phosphoric aci ...
/
hydrocarbon
In organic chemistry, a hydrocarbon is an organic compound consisting entirely of hydrogen and carbon. Hydrocarbons are examples of group 14 hydrides. Hydrocarbons are generally colourless and hydrophobic, and their odors are usually weak or ex ...
mixture to extract both uranium and plutonium from
nitric acid
Nitric acid is the inorganic compound with the formula . It is a highly corrosive mineral acid. The compound is colorless, but older samples tend to be yellow cast due to decomposition into oxides of nitrogen. Most commercially available nitri ...
. This extraction is of the
nitrate
Nitrate is a polyatomic ion
A polyatomic ion, also known as a molecular ion, is a covalent bonded set of two or more atoms, or of a metal complex, that can be considered to behave as a single unit and that has a net charge that is not zer ...
salts and is classed as being of a
solvation
Solvation (or dissolution) describes the interaction of a solvent with dissolved molecules. Both ionized and uncharged molecules interact strongly with a solvent, and the strength and nature of this interaction influence many properties of the ...
mechanism. For example, the extraction of plutonium by an extraction agent (S) in a nitrate medium occurs by the following reaction.
:Pu
4+aq + 4NO
3−aq + 2S
organic →
3)4S2">u(NO3)4S2sub>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
X-ray crystallography is the experimental science determining the atomic and molecular structure of a crystal, in which the crystalline structure causes a beam of incident X-rays to diffract into many specific directions. By measuring the angles ...
.
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
The actinide () or actinoid () series encompasses the 15 metallic chemical elements with atomic numbers from 89 to 103, actinium through lawrencium. The actinide series derives its name from the first element in the series, actinium. The inform ...
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
Ruthenium is a chemical element with the Symbol (chemistry), symbol Ru and atomic number 44. It is a rare transition metal belonging to the platinum group of the periodic table. Like the other metals of the platinum group, ruthenium is inert to ...
. The dibutyl hydrogen phosphate can make the system behave in a more complex manner as it tends to extract metals by an
ion exchange
Ion exchange is a reversible interchange of one kind of ion present in an insoluble solid with another of like charge present in a solution surrounding the solid with the reaction being used especially for softening or making water demineralised, ...
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
Sodium carbonate, , (also known as washing soda, soda ash and soda crystals) is the inorganic compound with the formula Na2CO3 and its various hydrates. All forms are white, odourless, water-soluble salts that yield moderately alkaline solutions ...
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
Radioactive waste is a type of hazardous waste that contains radioactive material. Radioactive waste is a result of many activities, including nuclear medicine, nuclear research, nuclear power generation, rare-earth mining, and nuclear weapons r ...
disposal sites, such as
Yucca Mountain nuclear waste repository
The Yucca Mountain Nuclear Waste Repository, as designated by the Nuclear Waste Policy Act amendments of 1987, is a proposed deep geological repository storage facility within Yucca Mountain for spent nuclear fuel and other high-level radioac ...
, by removing the uranium which makes up the vast majority of the mass and volume of used fuel and recycling it as
reprocessed uranium
Reprocessed uranium (RepU) is the uranium recovered from nuclear reprocessing, as done commercially in France, the UK and Japan and by nuclear weapons states' military plutonium production programs. This uranium makes up the bulk of the material s ...
.
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
Technetium is a chemical element with the symbol Tc and atomic number 43. It is the lightest element whose isotopes are all radioactive. All available technetium is produced as a synthetic element. Naturally occurring technetium is a spontaneous ...
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 scrubs sections of the process. The addition of AHA greatly diminishes the extractability of plutonium and
neptunium
Neptunium is a chemical element with the Symbol (chemistry), symbol Np and atomic number 93. A radioactivity, radioactive actinide metal, neptunium is the first transuranic element. Its position in the periodic table just after uranium, named after ...
, 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
Tributyl phosphate, known commonly as TBP, is an organophosphorus compound with the chemical formula (CH3CH2CH2CH2O)3PO. This colourless, odorless liquid finds some applications as an extractant and a plasticizer. It is an ester of phosphoric aci ...
, (TBP), the PUREX process can be turned into the TRUEX (''TR''ans''U''ranic ''EX''traction) process this is a process which was invented in the US 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 (''DIAM''ide''EX''traction) process has the advantage of avoiding the formation of organic waste which contains elements other than
carbon
Carbon () is a chemical element with the symbol C and atomic number 6. It is nonmetallic and tetravalent
In chemistry, the valence (US spelling) or valency (British spelling) of an element is the measure of its combining capacity with o ...
,
hydrogen
Hydrogen is the chemical element with the symbol H and atomic number 1. Hydrogen is the lightest element. At standard conditions hydrogen is a gas of diatomic molecules having the formula . It is colorless, odorless, tasteless, non-toxic, an ...
,
nitrogen
Nitrogen is the chemical element with the symbol N and atomic number 7. Nitrogen is a nonmetal and the lightest member of group 15 of the periodic table, often called the pnictogens. It is a common element in the universe, estimated at se ...
, and
oxygen
Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements as wel ...
. Such an organic waste can be burned without the formation of acidic gases which could contribute to
acid rain
Acid rain is rain or any other form of precipitation that is unusually acidic, meaning that it has elevated levels of hydrogen ions (low pH). Most water, including drinking water, has a neutral pH that exists between 6.5 and 8.5, but acid ...
. 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 (SANEX). As part of the management of minor actinides, it has been proposed that the
lanthanides
The lanthanide () or lanthanoid () series of chemical elements comprises the 15 metallic chemical elements with atomic numbers 57–71, from lanthanum through lutetium. These elements, along with the chemically similar elements scandium and yttr ...
and trivalent minor
actinides
The actinide () or actinoid () series encompasses the 15 metallic chemical elements with atomic numbers from 89 to 103, actinium through lawrencium. The actinide series derives its name from the first element in the series, actinium. The inform ...
should be removed from the PUREX
raffinate In chemical separation terminology, the raffinate (from French ''raffiner'', to refine) is a product which has had a component or components removed. The product having the removed materials is referred to as the extract. For example, in solvent ext ...
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
The lanthanide () or lanthanoid () series of chemical elements comprises the 15 metallic chemical elements with atomic numbers 57–71, from lanthanum through lutetium. These elements, along with the chemically similar elements scandium and yttr ...
must be removed. The lanthanides have 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-triazinyl pyridine (BTP) based process.
Other systems such as the dithiophosphinic acids are being worked on by some other workers.
This is the ''UNiversal'' ''EX''traction 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
The minor actinides are the actinide elements in used nuclear fuel other than uranium and plutonium, which are termed the major actinides. The minor actinides include neptunium (element 93), americium (element 95), curium (element 96), berkeli ...
)
radioisotopes
A radionuclide (radioactive nuclide, radioisotope or radioactive isotope) is a nuclide that has excess nuclear energy, making it unstable. This excess energy can be used in one of three ways: emitted from the nucleus as gamma radiation; transferr ...
from the raffinates left after the extraction of uranium and plutonium from used
nuclear fuel
Nuclear fuel is material used in nuclear power stations to produce heat to power turbines. Heat is created when nuclear fuel undergoes nuclear fission.
Most nuclear fuels contain heavy fissile actinide elements that are capable of undergoing ...
. The chemistry is based upon the interaction of
caesium
Caesium (IUPAC spelling) (or cesium in American English) is a chemical element with the symbol Cs and atomic number 55. It is a soft, silvery-golden alkali metal with a melting point of , which makes it one of only five elemental metals that a ...
and
strontium
Strontium is the chemical element with the symbol Sr and atomic number 38. An alkaline earth metal, strontium is a soft silver-white yellowish metallic element that is highly chemically reactive. The metal forms a dark oxide layer when it is ex ...
with poly
ethylene oxide
Ethylene oxide is an organic compound with the chemical formula, formula . It is a cyclic ether and the simplest epoxide: a three-membered Ring (chemistry), ring consisting of one oxygen atom and two carbon atoms. Ethylene oxide is a colorless a ...
(poly
ethylene glycol
Ethylene glycol (IUPAC name: ethane-1,2-diol) is an organic compound (a vicinal diol) with the formula . It is mainly used for two purposes, as a raw material in the manufacture of polyester fibers and for antifreeze formulations. It is an odo ...
) and a
cobalt
Cobalt is a chemical element with the symbol Co and atomic number 27. As with nickel, cobalt is found in the Earth's crust only in a chemically combined form, save for small deposits found in alloys of natural meteoric iron. The free element, pr ...
carborane
Carboranes are electron-delocalized (non-classically bonded) clusters composed of boron, carbon and hydrogen atoms.Grimes, R. N., ''Carboranes 3rd Ed.'', Elsevier, Amsterdam and New York (2016), . Like many of the related boron hydrides, these cl ...
anion
An ion () is an atom or molecule with a net electrical charge.
The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by convent ...
(known as chlorinated cobalt dicarbollide). The actinides are extracted by CMPO, and the
diluent
A diluent (also referred to as a filler, dilutant or thinner) is a Concentration, diluting agent. Certain fluids are too Viscosity, viscous to be pumped easily or too density, dense to flow from one particular point to the other. This can be prob ...
is a polar
aromatic
In chemistry, aromaticity is a chemical property of cyclic ( ring-shaped), ''typically'' planar (flat) molecular structures with pi bonds in resonance (those containing delocalized electrons) that gives increased stability compared to satur ...
such as
nitrobenzene
Nitrobenzene is an organic compound with the chemical formula C6H5 NO2. It is a water-insoluble pale yellow oil with an almond-like odor. It freezes to give greenish-yellow crystals. It is produced on a large scale from benzene as a precursor t ...
. Other diluents such as ''meta''-nitrobenzotri
fluoride
Fluoride (). According to this source, is a possible pronunciation in British English. is an inorganic, monatomic anion of fluorine, with the chemical formula (also written ), whose salts are typically white or colorless. Fluoride salts typ ...
and phenyl trifluoromethyl
sulfone
In organic chemistry, a sulfone is a organosulfur compound containing a sulfonyl () functional group attached to two carbon atoms. The central hexavalent sulfur atom is double-bonded to each of two oxygen atoms and has a single bond to each of ...
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. Like
chromate and
molybdate
In chemistry a molybdate is a compound containing an oxoanion with molybdenum in its highest oxidation state of 6. Molybdenum can form a very large range of such oxoanions which can be discrete structures or polymeric extended structures, althoug ...
, the
99TcO
4 anion can react with steel surfaces to form a
corrosion
Corrosion is a natural process that converts a refined metal into a more chemically stable oxide. It is the gradual deterioration of materials (usually a metal) by chemical or electrochemical reaction with their environment. Corrosion engine ...
resistant layer. In this way, these metaloxo anions act as
anodic
An anode is an electrode of a polarized electrical device through which conventional current enters the device. This contrasts with a cathode, an electrode of the device through which conventional current leaves the device. A common mnemonic is ...
corrosion inhibitor
In chemistry, a corrosion inhibitor or anti-corrosive is a chemical compound that, when added to a liquid or gas, decreases the corrosion rate of a material, typically a metal or an alloy, that comes into contact with the fluid. The effectiveness ...
s. The formation of
99TcO
2 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 (e.g.
submarine
A submarine (or sub) is a watercraft capable of independent operation underwater. It differs from a submersible, which has more limited underwater capability. The term is also sometimes used historically or colloquially to refer to remotely op ...
reactors lost at sea). This
99TcO
2 layer renders the steel surface passive, inhibiting the
anodic
An anode is an electrode of a polarized electrical device through which conventional current enters the device. This contrasts with a cathode, an electrode of the device through which conventional current leaves the device. A common mnemonic is ...
corrosion
Corrosion is a natural process that converts a refined metal into a more chemically stable oxide. It is the gradual deterioration of materials (usually a metal) by chemical or electrochemical reaction with their environment. Corrosion engine ...
reaction. The radioactive nature of technetium makes this corrosion protection impractical in almost all situations. It has also been shown that
99TcO
4 anions react to form a layer on the surface of activated carbon (
charcoal
Charcoal is a lightweight black carbon residue produced by strongly heating wood (or other animal and plant materials) in minimal oxygen to remove all water and volatile constituents. In the traditional version of this pyrolysis process, cal ...
) or
aluminium
Aluminium (aluminum in American and Canadian English) is a chemical element with the symbol Al and atomic number 13. Aluminium has a density lower than those of other common metals, at approximately one third that of steel. I ...
. A short review of the biochemical properties of a series of key long lived radioisotopes can be read on line.
99Tc in nuclear waste may exist in chemical forms other than the
99TcO
4 anion, these other forms have different chemical properties.
Similarly, the release of iodine-131 in a serious power reactor accident could be retarded by absorption on metal surfaces within the nuclear plant.
Education
Despite the growing use of nuclear medicine, the potential expansion of nuclear power plants, and worries about protection against nuclear threats and the management of the nuclear waste generated in past decades, the number of students opting to specialize in nuclear and radiochemistry has decreased significantly over the past few decades. Now, with many experts in these fields approaching retirement age, action is needed to avoid a workforce gap in these critical fields, for example by building student interest in these careers, expanding the educational capacity of universities and colleges, and providing more specific on-the-job training.
Nuclear and Radiochemistry (NRC) is mostly being taught at university level, usually first at the Master- and PhD-degree level. In Europe, as substantial effort is being done to harmonize and prepare the NRC education for the industry's and society's future needs. This effort is being coordinated in a project funded by the Coordinated Action supported by the European Atomic Energy Community's 7th Framework Program. Although NucWik is primarily aimed at teachers, anyone interested in nuclear and radiochemistry is welcome and can find a lot of information and material explaining topics related to NRC.
Spinout areas
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
Geology () is a branch of natural science concerned with Earth and other astronomical objects, the features or rocks of which it is composed, and the processes by which they change over time. Modern geology significantly overlaps all other Ear ...
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 is changed by making an isotopic modification of a substrate, known as the
kinetic isotope effect
In physical organic chemistry, a kinetic isotope effect (KIE) is the change in the reaction rate of a chemical reaction when one of the atoms in the reactants is replaced by one of its isotopes. Formally, it is the ratio of rate constants for th ...
. This is now a standard method in
organic chemistry
Organic chemistry is a subdiscipline within chemistry involving the scientific study of the structure, properties, and reactions of organic compounds and organic materials, i.e., matter in its various forms that contain carbon atoms.Clayden, J.; ...
. Briefly, replacing normal hydrogen (
protons
A proton is a stable subatomic particle, symbol , H+, or 1H+ with a positive electric charge of +1 ''e'' elementary charge. Its mass is slightly less than that of a neutron and 1,836 times the mass of an electron (the proton–electron mass ...
) by
deuterium
Deuterium (or hydrogen-2, symbol or deuterium, also known as heavy hydrogen) is one of two Stable isotope ratio, stable isotopes of hydrogen (the other being Hydrogen atom, protium, or hydrogen-1). The atomic nucleus, nucleus of a deuterium ato ...
within a molecule causes the
molecular vibration
A molecular vibration is a periodic motion of the atoms of a molecule relative to each other, such that the center of mass of the molecule remains unchanged. The typical vibrational frequencies range from less than 1013 Hz to approximately 1014 Hz ...
al frequency of X-H (for example C-H, N-H and O-H) bonds to decrease, which leads to a decrease in vibrational
zero-point energy
Zero-point energy (ZPE) is the lowest possible energy that a quantum mechanical system may have. Unlike in classical mechanics, quantum systems constantly Quantum fluctuation, fluctuate in their lowest energy state as described by the Heisen ...
. This 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
Cosmogenic nuclides (or cosmogenic isotopes) are rare nuclides (isotopes) created when a high-energy cosmic ray interacts with the atomic nucleus, nucleus of an ''in situ'' Solar System atom, causing nucleons (protons and neutrons) to be expelled ...
are formed by the interaction of
cosmic rays
Cosmic rays are high-energy particles or clusters of particles (primarily represented by protons or atomic nuclei) that move through space at nearly the speed of light. They originate from the Sun, from outside of the Solar System in our own ...
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
Isotope geochemistry is an aspect of geology based upon the study of natural variations in the relative abundances of isotopes of various elements. Variations in isotopic abundance are measured by isotope ratio mass spectrometry, and can reveal ...
and
Isotopic signature
An isotopic signature (also isotopic fingerprint) is a ratio of non-radiogenic ' stable isotopes', stable radiogenic isotopes, or unstable radioactive isotopes of particular elements in an investigated material. The ratios of isotopes in a sample m ...
for further details).
Biology
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
Metabolism (, from el, μεταβολή ''metabolē'', "change") is the set of life-sustaining chemical reactions in organisms. The three main functions of metabolism are: the conversion of the energy in food to energy available to run cell ...
of an organism converts one substance to another. For instance a
green plant
Viridiplantae (literally "green plants") are a clade of eukaryote, eukaryotic organisms that comprise approximately 450,000–500,000 species and play important roles in both terrestrial and aquatic ecosystems. They are made up of the green alga ...
uses light
energy
In physics, energy (from Ancient Greek: ἐνέργεια, ''enérgeia'', “activity”) is the quantitative property that is transferred to a body or to a physical system, recognizable in the performance of work and in the form of heat a ...
to convert water and
carbon dioxide
Carbon dioxide (chemical formula ) is a chemical compound made up of molecules that each have one carbon atom covalently double bonded to two oxygen atoms. It is found in the gas state at room temperature. In the air, carbon dioxide is transpar ...
into glucose by
photosynthesis
Photosynthesis is a process used by plants and other organisms to convert light energy into chemical energy that, through cellular respiration, can later be released to fuel the organism's activities. Some of this chemical energy is stored i ...
. 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
A chloroplast () is a type of membrane-bound organelle known as a plastid that conducts photosynthesis mostly in plant cell, plant and algae, algal cells. The photosynthetic pigment chlorophyll captures the energy from sunlight, converts it, ...
within the plant cells.
For biochemical and physiological experiments and medical methods, a number of specific isotopes have important applications.
*Stable isotopes have the advantage of not delivering a radiation dose to the system being studied; however, a significant excess of them in the organ or organism might still interfere with its functionality, and the availability of sufficient amounts for whole-animal studies is limited for many isotopes. Measurement is also difficult, and usually requires
mass spectrometry
Mass spectrometry (MS) is an analytical technique that is used to measure the mass-to-charge ratio of ions. The results are presented as a ''mass spectrum'', a plot of intensity as a function of the mass-to-charge ratio. Mass spectrometry is use ...
to determine how much of the isotope is present in particular compounds, and there is no means of localizing measurements within the cell.
*
2H (deuterium), the stable isotope of hydrogen, is a stable tracer, the concentration of which can be measured by mass spectrometry or NMR. It is incorporated into all cellular structures. Specific deuterated compounds can also be produced.
*
15N, a stable isotope of nitrogen, has also been used. It is incorporated mainly into proteins.
*Radioactive isotopes have the advantages of being detectable in very low quantities, in being easily measured by
scintillation counting Liquid scintillation counting is the measurement of radioactive activity of a sample material which uses the technique of mixing the active material with a liquid scintillator (e.g. zinc sulfide), and counting the resultant photon emissions. The pu ...
or other radiochemical methods, and in being localizable to particular regions of a cell, and quantifiable by
autoradiography
An autoradiograph is an image on an X-ray film or nuclear emulsion produced by the pattern of decay emissions (e.g., beta particles or gamma rays) from a distribution of a radioactive substance. Alternatively, the autoradiograph is also available ...
. Many compounds with the radioactive atoms in specific positions can be prepared, and are widely available commercially. In high quantities they require precautions to guard the workers from the effects of radiation—and they can easily contaminate laboratory glassware and other equipment. For some isotopes the half-life is so short that preparation and measurement is difficult.
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
Palladium is a chemical element with the symbol Pd and atomic number 46. It is a rare and lustrous silvery-white metal discovered in 1803 by the English chemist William Hyde Wollaston. He named it after the asteroid Pallas, which was itself na ...
catalysed
carbonylation
Carbonylation refers to reactions that introduce carbon monoxide into organic and inorganic substrates. Carbon monoxide is abundantly available and conveniently reactive, so it is widely used as a reactant in industrial chemistry. The term carbon ...
reaction in a
microfluidic
Microfluidics refers to the behavior, precise control, and manipulation of fluids that are geometrically constrained to a small scale (typically sub-millimeter) at which surface forces dominate volumetric forces. It is a multidisciplinary field tha ...
device has been used to rapidly form amides and it might be possible to use this method to form radioactive imaging agents for
PET
A pet, or companion animal, is an animal kept primarily for a person's company or entertainment rather than as a working animal, livestock, or a laboratory animal. Popular pets are often considered to have attractive appearances, intelligence, ...
imaging.
*
3H (
tritium
Tritium ( or , ) or hydrogen-3 (symbol T or H) is a rare and radioactive isotope of hydrogen with half-life about 12 years. The nucleus of tritium (t, sometimes called a ''triton'') contains one proton and two neutrons, whereas the nucleus o ...
), the radioisotope of hydrogen, is available at very high specific activities, and compounds with this isotope in particular positions are easily prepared by standard chemical reactions such as hydrogenation of unsaturated precursors. The isotope emits very soft beta radiation, and can be detected by scintillation counting.
*
11C, carbon-11 is usually produced by
cyclotron
A cyclotron is a type of particle accelerator invented by Ernest O. Lawrence in 1929–1930 at the University of California, Berkeley, and patented in 1932. Lawrence, Ernest O. ''Method and apparatus for the acceleration of ions'', filed: Janu ...
bombardment of
14N with protons. The resulting nuclear reaction is .
Additionally, carbon-11 can also be made using a
cyclotron
A cyclotron is a type of particle accelerator invented by Ernest O. Lawrence in 1929–1930 at the University of California, Berkeley, and patented in 1932. Lawrence, Ernest O. ''Method and apparatus for the acceleration of ions'', filed: Janu ...
;
boron
Boron is a chemical element with the symbol B and atomic number 5. In its crystalline form it is a brittle, dark, lustrous metalloid; in its amorphous form it is a brown powder. As the lightest element of the ''boron group'' it has th ...
in the form of
boric oxide
Boron trioxide or diboron trioxide is the oxide of boron with the formula . It is a colorless transparent solid, almost always glassy (amorphous), which can be crystallized only with great difficulty. It is also called boric oxide or boria. It h ...
is reacted with
protons
A proton is a stable subatomic particle, symbol , H+, or 1H+ with a positive electric charge of +1 ''e'' elementary charge. Its mass is slightly less than that of a neutron and 1,836 times the mass of an electron (the proton–electron mass ...
in a (p,n) reaction. Another alternative route is to react
10B with deuterons. By rapid organic synthesis, the
11C compound formed in the cyclotron is converted into the imaging agent which is then used for PET.
*
14C, carbon-14 can be made (as above), and it is possible to convert the target material into simple inorganic and organic compounds. In most
organic synthesis
Organic synthesis is a special branch of chemical synthesis and is concerned with the intentional construction of organic compounds. Organic molecules are often more complex than inorganic compounds, and their synthesis has developed into one o ...
work it is normal to try to create a product out of two approximately equal sized fragments and to use a convergent route, but when a radioactive label is added, it is normal to try to add the label late in the synthesis in the form of a very small fragment to the molecule to enable the radioactivity to be localised in a single group. Late addition of the label also reduces the number of synthetic stages where radioactive material is used.
*
18F, fluorine-18 can be made by the reaction of
neon
Neon is a chemical element with the symbol Ne and atomic number 10. It is a noble gas. Neon is a colorless, odorless, inert monatomic gas under standard conditions, with about two-thirds the density of air. It was discovered (along with krypton ...
with deuterons,
20Ne reacts in a (d,
4He) reaction. It is normal to use neon gas with a trace of stable
fluorine
Fluorine is a chemical element with the symbol F and atomic number 9. It is the lightest halogen and exists at standard conditions as a highly toxic, pale yellow diatomic gas. As the most electronegative reactive element, it is extremely reacti ...
(
19F
2). The
19F
2 acts as a carrier which increases the yield of radioactivity from the cyclotron target by reducing the amount of radioactivity lost by absorption on surfaces. However, this reduction in loss is at the cost of the specific activity of the final product.
Nuclear spectroscopy
Nuclear spectroscopy Nuclear spectroscopy is a superordinate concept of methods that uses properties of a nucleus to probe material properties. By emission or absorption of radiation from the nucleus information of the local structure is obtained, as an interaction of ...
are methods that use the nucleus to obtain information of the local structure in matter. Important methods are NMR (see below),
Mössbauer spectroscopy
Mössbauer spectroscopy is a spectroscopic technique based on the Mössbauer effect. This effect, discovered by Rudolf Mössbauer (sometimes written "Moessbauer", German: "Mößbauer") in 1958, consists of the nearly recoil-free emission and abso ...
and
Perturbed angular correlation
The perturbed γ-γ angular correlation, PAC for short or PAC-Spectroscopy, is a method of nuclear solid-state physics with which magnetic and electric fields in crystal structures can be measured. In doing so, electrical field gradients and the L ...
. These methods use the interaction of the
hyperfine field with the nucleus' spin. The field can be magnetic or/and electric and are created by the electrons of the atom and its surrounding neighbours. Thus, these methods investigate the local structure in matter, mainly
condensed matter
Condensed matter physics is the field of physics that deals with the macroscopic and microscopic physical properties of matter, especially the solid and liquid phases which arise from electromagnetic forces between atoms. More generally, the su ...
in
condensed matter physics
Condensed matter physics is the field of physics that deals with the macroscopic and microscopic physical properties of matter, especially the solid and liquid phases which arise from electromagnetic forces between atoms. More generally, the sub ...
and
solid state chemistry Solid-state chemistry, also sometimes referred as materials chemistry, is the study of the synthesis, structure, and properties of solid phase materials, particularly, but not necessarily exclusively of, non-molecular solids. It therefore has a str ...
.
Nuclear magnetic resonance (NMR)
NMR spectroscopy
Nuclear magnetic resonance spectroscopy, most commonly known as NMR spectroscopy or magnetic resonance spectroscopy (MRS), is a spectroscopic technique to observe local magnetic fields around atomic nuclei. The sample is placed in a magnetic fiel ...
uses the net spin of nuclei in a substance upon energy absorption to identify molecules. This has now become a standard spectroscopic tool within
synthetic chemistry
As a topic of chemistry, chemical synthesis (or combination) is the artificial execution of chemical reactions to obtain one or several products. This occurs by physical and chemical manipulations usually involving one or more reactions. In mod ...
. One major use of NMR is to determine the
bond
Bond or bonds may refer to:
Common meanings
* Bond (finance), a type of debt security
* Bail bond, a commercial third-party guarantor of surety bonds in the United States
* Chemical bond, the attraction of atoms, ions or molecules to form chemical ...
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.
See also
*
Important publications in nuclear chemistry
*
Nuclear physics
Nuclear physics is the field of physics that studies atomic nuclei and their constituents and interactions, in addition to the study of other forms of nuclear matter.
Nuclear physics should not be confused with atomic physics, which studies the ...
*
Nuclear spectroscopy Nuclear spectroscopy is a superordinate concept of methods that uses properties of a nucleus to probe material properties. By emission or absorption of radiation from the nucleus information of the local structure is obtained, as an interaction of ...
References
Further reading
;''Handbook of Nuclear Chemistry''
:Comprehensive handbook in six volumes by 130 international experts. Edited by Attila Vértes, Sándor Nagy, Zoltán Klencsár, Rezső G. Lovas, Frank Rösch.
Springer 2011.
;''Radioactivity Radionuclides Radiation''
:Textbook by Magill, Galy. , Springer
2005
;''Radiochemistry and Nuclear Chemistry, 3rd Ed''
:Comprehensive textbook by Choppin,
Liljenzin and Rydberg. , Butterworth-Heinemann, 200
;''Radiochemistry and Nuclear Chemistry, 4th Ed''
:Comprehensive textbook by Choppin,
Liljenzin, Rydberg and Ekberg. , Elsevier Inc., 2013
;''Radioactivity, Ionizing radiation and Nuclear Energy''
:Basic textbook for undergraduates by Jiri Hála and James D Navratil. , Konvoj, Brno 200
;''The Radiochemical Manual''
:Overview of the production and uses of both open and sealed sources. Edited by BJ Wilson and written by RJ Bayly, JR Catch, JC Charlton, CC Evans, TT Gorsuch, JC Maynard, LC Myerscough, GR Newbery, H Sheard, CBG Taylor and BJ Wilson. The radiochemical centre (Amersham) was sold via
HMSO
The Office of Public Sector Information (OPSI) is the body responsible for the operation of His Majesty's Stationery Office (HMSO) and of other public information services of the United Kingdom. The OPSI is part of the National Archives of the Un ...
, 1966 (second edition)
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Chemistry