This book aims to provide the reader with a detailed description of the basic princi­ples and applications of nuclear and radiochemistry. Its content is based on the authors’ more than 50 and 25 years of experience, respectively, as professors of nuclear and radiochemistry at both the B. Sc. and M. Sc. levels in the Isotope Laboratory of the Department of Colloid and Environmental Chemistry at the University of Debrecen, Hungary.

Although the book contains all modern aspects of nuclear and radiochemistry, it still has a characteristic local flavor. Special attention is paid to the thermodynam­ics of radioisotope tracer methods and to the very diluted systems (carrier-free radioactive isotopes), to the principles of chemical processes with unsealed radioac­tive sources, and to the physical and mathematical aspects of radiochemistry. This approach originates from the first professor of the Isotope Laboratory, Lajos Imre, who himself was Otto Hahn’s disciple and coworker.

The material is divided into 14 chapters. Chapters 1—6 discuss the basic con­cepts of nuclear and radiochemistry and Chapters 7—14 deal with the applications of radioactivity and nuclear processes. There are separate chapters dedicated to the main branches of modern radiochemistry: nuclear medicine and nuclear power plants, including the problems of the disposal of nuclear wastes. One chapter (Chapter 10) deals with nuclear analysis (both bulk and surface analyses), including the analytical methods based on the interactions of radiation with matter.

As mentioned previously, the authors have extensive experience in teaching nuclear and radiochemistry. Therefore, we have had the chance to work with many exceptional students and excellent colleagues. Many thanks for their contributions. We are grateful for their assistance in the improvement of our educational work and the useful discussions that helped to advance our understanding in this field.

We thank our colleagues who have contributed to this book, namely, Dr. Lajos Baranyai (Chapter 11 and Section 8.7) and Dr. jozsef Varga (Chapter 12). Many thanks to Dr. Szabolcs Vass and Dr. Jozsef Konya (a physician and an associate professor) for their assistance in the fields of neutron diffraction and the biological effects of radiation, respectively. Thanks also to those colleagues, namely, Prof. Laszlo Bartha, Prof. Dezso Beke, Dr. Istvan Csige, Prof. Julius Csikai, Prof. Bela Kanyar, Dr. Aniko Kerkapoly, Dr. Zsofia Kertesz, Dr. Peter Kovacs-Palffy, Dr. Laszlo Kover, Prof. Erno Kuzmann, Boglarka Makai, Katalin Nagy, Zoltan Nemes, Dr. Katalin Papp, Dr. Peter Raics, Dr. Zsolt Revay, Dr. Laszlo Szentmiklosi, Dr. Edit Szilagyi, Dr. Nora Vajda, who have provided excellent representative photo­graphs, figures, data, and so on. Prof. Julius Csikai provided the beautiful photograph

on the book cover. Thanks to Zoltan Major for the improvement of the quality of the photograph.

We thank Dr. Klara Konya for the critical reading of the manuscript and for her remarks and corrections.

The work is supported by the TAMOP 4.2.1./B-09/1/KONV-2010-0007 project. The project is cofinanced by the European Union and the European Social Fund.

We recommend this book to students in chemistry, chemical engineering, envi­ronmental sciences, and specialists working with radiochemistry in industry, agri­culture, geology, medicine, physics, analytics, and to those in other fields.

jOzsef Konya and Noemi M. Nagy

December 2011, Debrecen (Hungary)

Introduction

From the dawn of natural sciences, scientists and philosophers have reflected on the nature of matter. In the end of the nineteenth century, the discoveries signed by Lavoisier, Dalton, and Avogadro (namely, the law of conservation of mass, the atomic theory, and the definition of a mole as a unit of the chemical quantity) led to a plausible model. This model was built on the principles of Dalton’s atomic theory, which states that:

• all matter is composed of small particles called atoms,

• each element is composed of only one chemically distinct type of atom,

• that all atoms of an element are identical, with the same mass, size, and chemical beha­vior, and

• that atoms are tiny, indivisible, and indestructible particles.

In the same period, the basic laws of thermodynamics have been postulated. The first law of thermodynamics is an expression of the principle of conservation of energy.

This model of the matter has been challenged when it was discovered that the same element can have radioactive and stable forms (i. e., an element can have atoms of different mass). The discovery of the radioactivity is linked to Henri Becquerel’s name and to the outcome of his experiments which were presented in 1896 at the conference of the French Academy and published in Comptes Rendus e I’Academie des Sciences.

Following his family tradition (his father and grandfather also studied fluores­cence, and his father, Edmund Becquerel, studied the fluorescence of uranium salts), Becquerel examined the fluorescent properties of potassium uranyl sulfate [K2UO2(SO4)2 • 2H2O]. Since Wilhelm Rontgen’s previous studies, it has been known that X-rays can be followed by phosphorescent light emitted by the wall of the X-ray tube, and Becquerel wanted to see if this process could be reversed,

i. e., if phosphorescent light can produce X-rays. After exposing potassium uranyl sulfate to sunlight, he wrapped it in black paper, placed it on a photographic plate, and observed the “X-ray.” He repeated the experiments with and without exposure to sunlight and obtained the same result: the blackening of the photographic plate. He has concluded that the blackening of the photographic plate was not caused by fluorescence induced by sunlight, but rather by an intrinsic property of the uranium salt. This property was first called Becquerel rays, and later it was termed

Nuclear and Radiochemistry. DOI: http://dx. doi. org/10.1016/B978-0-12-391430-9.00001-9

© 2012 Elsevier Inc. All rights reserved.

“radioactive radiation[1].” Becquerel also has observed that electroscope loses its charge under the effect of this radiation because the radiation induces charges in the air.

The same radiation was observed by Pierre Curie and Marie Curie, as well as G. Schmidt in Germany using thorium salts. They have found that the ores of uranium and thorium have more intense radiation than the pure salts: for example, pitchblende from Johanngeorgenstadt and Joachimstal has about five and four times more intense radiation, respectively, than black uranium oxide (U3Og). This more intense radiation originates from elements that were not present in the pure salts, which later were identified as the new radioactive elements polonium and radium, and which were separated from uranium ore in Joachimstal. The Curies presented the results at the French Academy in 1898 and published in Comptes Rendus e I’Academie des Sciences. As proposed by Marie Curie, the first new radioactive element, polonium, was named after her homeland of Poland. In the Curies’ laboratory, radioactivity was detected by the ionization current produced by the radiation. In 1902, the Curies produced 100 mg of radium and determined the atomic mass, which they later corrected (226.5 g/mol). Marie Curie produced metallic radium by electrolysis of molten salts in 1910.

Rutherford has differentiated three types of radiation (alpha, beta, and gamma) by using absorption experiments in 1889. He also determined that the radiations had very high energy. In 1903, Rutherford and Soddy concluded that the radioac­tive elements are undergoing spontaneous transformation from one chemical atom into another and that the radioactive radiation was an accompaniment of these tran­sitions. Radioactive elements were called radioelements. Since they were not known earlier, and therefore did not have names, some of them were named by adding letters to the name of the original (i. e., parent) element (e. g., UX, ThX). Others were given new names (such as radium, polonium, radium emanation-today radon).

The discovery of radium and polonium filled two empty places on the periodic table. Later studies, however, showed that some radioactive elements had the same chemical properties as known stable elements—they differed only in the amount of radioactivity. Therefore, they should be put in places in the periodic table that are already filled, which is impossible according to Dalton’s atomic theory. For exam­ple, different types of thorium (thorium, UX1, iononium (Io), radioactinium, today Th-232, Th-234, Th-230, and Th-227, respectively) and radium (radium, mesotho — rium1, ThX, AcX, today Ra-226, Ra-228, Ra-224, or Ra-223, respectively) atoms have been recognized.

These experimental results presented serious contractions to the Daltonian model of matter and the principle of the conservation of mass and energy. Einstein

has solved part of these contradictions using the law of the equivalence of energy and mass:

2

E = mc

where E is the energy of the system, m is the mass, and c means the velocity of light in a vacuum.

As the interpretation of the other part of the contradictions, Soddy defined the term “isotopes,” neglecting the postulate in Dalton’s theory on the identity of the atoms of an element. Accordingly, isotopes are atoms of the same element having different masses.

What kind of scientific and practical importance did these discoveries have? At first, they formed the basis of the modern atomic theory, resulting in the develop­ment of new fields and explaining some phenomena. For example, nucleogenesis, the formation of the elements in the universe, now can be explained based on the principles of natural sciences, attempting to give a philosophical significance of the “creation.”

From the beginning, the practical importance has been underestimated. In 1898, however, radium found its role in cancer therapy. In 1933 in the Royal Society meeting, Rutherford said that “any talk of atomic energy” was “moonshine.” Rutherford’s statement inspired Leo Szilard to devise the principle of the nuclear chain reaction, which was experimentally discovered by Otto Hahn in 1938. The chain reaction of uranium fission led to the production of nuclear power plants, and, unfortunately, nuclear weapons as well. However, in the future, the production of cheap, safe atomic energy can play a significant role in supplying energy.

3. Natural radioactive isotopes continuously producing in the nuclear reactions of the atoms of air (nitrogen, oxygen, argon) with cosmic radiation, for example, 3H, 7’10Be, 14C, 22Na, 26Al, 32’33P, 35S, 36Cl, 39Ar.

As the practical applications of radioactivity, tracer methods, activation analysis, nuclear medicine, and radiation therapy can be mentioned. As mentioned previ­ously, radioactivity has been discovered to be a natural process. Therefore, it is not an artificial product as believed by many. The environmental radioactive isotopes can be classified into three groups:

As previously discussed, many of these elements have naturally occurring radio­active isotopes.

The main stages of the history of nuclear science are summarized in Table 1.1, including the Nobel prizes gained by the scientists working in this field. In addi­tion, the chapters of this book related to the given stages are also listed.

Year	Discovery	Researcher(s)/county(ies)	Nobel Prize	In This Book
1895	X-ray	W. Rontgen	1901	This chapter
1896	Radioactivity by the radiation of uranium salt	H. Becquerel	1903	This chapter
1898	Polonium and radium	P. and M. Curie	1903	This chapter
1899	Radioactivity is caused by the decomposition of atoms	J. Elster and H. Geitel		This chapter
1900	Gamma radiation is considered as electromagnetic radiation	P. Villard and H. Becquerel, proved in 1914 by E. Rutherford and E. Andrade		Section 4.6 in Chapter 4
1900	Beta decay consists of electrons	H. Becquerel		Section 4.2 in Chapter 4
1902	Preparation of radium	P. and M. Curie, Debierne	1911	This chapter
1903	Alpha radiation consists of the ions of helium	E. Rutherford	1908	Section 4.1 in Chapter 4
1903	Radon (radium emanation)	W. Ramsay and F. Soddy	1904	Section 4.2, Section 8.5.1
1898-1902	Radiation has chemical and biological effects	P. Curie, A. Debierne, H. Becquerel, H. Danlos, and others		Section 13.4
1896-1905	Genetic relation of the radioelements	H. Becquerel, E. Rutherford, F. Soddy, B. Boltwood, and others		Section 4.2
1905	Equivalence of energy and mass	A. Einstein		This chapter
1907	Therapeutic application of radium	T. Stenbeck		Section 8.5.1
1909	Alpha scattering experiments: discovery of nucleus	H. Geiger and E. Mardsen		Section 5.2.2
1909	Terms of isotopes	F. Soddy	1921	Chapter 3

Determination of atomic mass by deviation in	J. J. Thomson		Section 3.1.1
electric and magnetic field
Rutherford’s atomic model	E. Rutherford		Section 2.1.1, Section 5.2.2
Radioactive indication	G. Hevesy and F. Paneth	1943	Chapters 8—12
Cloud chamber	C. T. Wilson	1927	Section 14.5.1
Cosmic radiation	V. F. Hess	1936	Section 2.2, Section 13.4.3
Interpretation of the decay series by using	K. Fajans and F. Soddy		Section 4.2
isotopes
Separation of neon isotopes using the deviation	F. W. Aston	1922	Section 3.1.1
in electric and magnetic field
Nucleus is surrounded by electrons moving on	N. Bohr	1922
orbitals with well-determined energy
Determination of the size and charge of atomic	H. Geiger and E. Mardsen		Section 2.1.1, Section 5.2.2
nuclei
Counter for radioactivity measurement	H. Geiger		Section 14.1
The first nuclear reaction:	E. Rutherford		Chapter 6
4He 114N! 17O 1 1H
Mass spectrometer	F. W. Aston	1922	Section 3.1.1
Isomer nuclei: 234mPa(UX2)234Pa(UZ)	O. Hahn		Section 4.4.6
Separation of isotopes by distillation	J. N. Bronsted and G. Hevesy		Section 3.2
Inelastic scattering of gamma photons	A. H. Compton	1927	Section 5.4.3
Wave-particle duality of moving particles	L. De Broglie		Section 4.4.1, Section 5.5.3, Section 6.1, Section 10.2.2.4
The radioactive tracer (Po) in biological research	A. Lacassagne and J. S. Lates		Section 8.5.1
The exclusion principle	W. Pauli	1945	Section 2.3
Wave mechanics in quantum theory	E. Schrodinger	1933	Section 4.4.1

1910 1911 1912 1912 1913 1913 1913 1913 1913 1913 1919 1919 1921 1921 1923 1924 1924 1925 1926

Researcher(s)/county(ies) Nobel In This Book

Prize

Experimental confirmation of the wave-particle duality	C. J. Davisson, L. H. Germer, and G. P. Thomson		Section 4.4.1
The uncertainty principle	W. Heisenberg	1932	Section 2.1.1
The Geiger—MUller counter	H. Geiger and W. Muller		Section 14.1
A high-voltage generator for acceleration of	R. J. Van de Graaf		Section 6.2.3
ions
Cyclotron	E. Lawrence and M. S. Livingston		Section 6.2.3, Section 8.5.2
Deuterium; isotope enrichment by evaporation	H. Urey	1934	Chapter 3.2
of liquid hydrogen
Neutron	J. Chadwick	1935	Section 2.1, Section 5.5.3
Nucleus: protons 1 neutrons	W. Heisenberg		Section 2.1
Positron	C. D. Andersson	1936	Section 4.2.2
Nuclear reactions with accelerated charged particles	J. D. Cockcroft and E. D.S. Walton	1951	Section 6.2.3
Isotopic effects in chemical reactions	H. Urey and D. Rittenberg		Sections 3.1.4 and 3.1.5
Pair formation	I. Curie and F. Joliot-Curie		Section 5.4.5
Magnetic momentum of proton	O. Stern	1943	Section 2.3
Nuclear studies by improved cloud chamber	P. M.S. Blackett	1948	Section 14.5.1
Symmetry principles of the nucleus	E. P. Wigner	1963	Section 2.3

1927 1927 1928 1931 1932 1932 1932 1932 1932 1932 1933 1933 1933 1931 1931

1934	Annihilation	M. Thibaud and F. Joliot — Curie		Section 5.3.3
1934	Artificial radioactivity: 4He 1 27Al! 30P 1 n	F. Joliot-Curie and I. Curie	1935	Chapter 6
1934	Discovery of Cherenkov radiation	P. A. Cserenkov, I. M. Frank, and I. E. Tamm	1958	Section 5.3.2
1935	Postulation of mesons	H. Yukawa	1949	Section 2.2
1935	Semiempirical formula for the binding energy of nuclei	C. F. Weizsacker		Section 2.5.1
1935-1936	Description of nuclear reactions with neutrons	E. Fermi	1938	Section 6.2.1
1936	Neutron activation analysis (NAA)	G. Hevesy and H. Levi		Section 10.2.2.1
1937 1937	Principle of Cherenkov radiation Technetium	P. A. Cserenkov, I. M. Frank, and I. E. Tamm G. Perrier and E. Segre	1958	Section 5.3.2
1937	p-Mesons in cosmic radiation	S. Neddermeyer and C. D. Andersson		Section 2.2
1938	Theory of nuclear fusion in stars	H. A. Bethe and C. F. Weizsacker	1967	Section 6.2.5
1938	Fission of uranium using neutrons	O. Hahn and F. Strassman	1944	Section 6.2.1
1938	Photomultiplier	Z. Bay		Section 14.2.2
1930-1939	Magnetic properties of nucleus	I. I. Rabi	1944	Section 2.3
1940 1940	First transuranium elements—neptunium and plutonium; chemistry of the transuranium elements; fission of plutonium-239 using neutrons Fission of 235U by thermal neutrons; 232Th and 238U by fast neutrons produce two to three new neutrons and release a high amount of energy	E. M. McMillan, G. T. Seaborg	1951	Section 6.2.6; the production of the additional transuranium elements are summarized in Table 6.3 Section 6.2.1
1942	First nuclear reactor	E. Fermi and coworkers		Section 7.1.3
1944	Self-sustaining fission of uranium	Germany		Section 7.1

Year	Discovery	Researcher(s)/county(ies)	Nobel Prize	In This Book
1945	Production of plutonium in kilograms. Application of nuclear weapons by the United States	Japan (Hiroshima, Nagasaki)		Section 7.5
1946-1948	Magnetic momentum of the nucleus	F. Bloch and E. M. Purcell	1952	Section 2.3
1949	Radiocarbon dating	W. Libby	1960	Section 4.3.6
1950	Shell model of nuclei	M. G. Mayer, O. Haxel, J. H.D. Jensen, and H. E. Suess	1963	Section 2.5.2
1951	First breeder and energy production reactor	Argonne National Laboratory (Idaho, USA)		Section 7.1
1951 1951 1951	Positronium atom Application of Co-60 in therapy of cancer Measurement of the time less than 10-6 s of the excited state in the nucleus by scintillation counter	M. Deutsch		Section 5.3.3 Chapter 12
1952	Bubble chamber	D. A. Glaser	1960	Section 14.5.1
1952	The first uncontrolled fusion reaction (hydrogen bomb)	United States		Section 7.5
1952	The first atomic bomb experiment by Great Britain	Australia		Section 7.5
1953	Collective motion of the nucleons in the nucleus	A. N. Bohr, B. R. Mattelson, and	1975	Section 2.5.3

L. J. Rainwater

1953 1953	The first atomic bomb experiment by Soviet Union Establishment of European Organization of Nuclear Research (CERN)	Soviet Union Twelve countries		Section 7.5
1953-1955	Unified nuclear model	A. Bohr, B. R. Mottelson, and S. G. Nilsson		Section 2.5.3
1953-1960	Electron scattering on the nucleus	R. Hofstadter	1961	Section 10.2.1
1953-1960	Experimental detection of neutrinos	F. Reines	1995	Section 4.4.2
1954-1958 1955	Electron spectroscopy Nuclear-powered submarine (Nautilus)	K. M. Siegbahn	1981	Section 10.2.1
1954-1956	5 MWe energy production reactor in Obnyiszkban	Soviet Union		Chapter 7
1955-1960	Neutron spectroscopy and diffraction	B. N. Brockhouse C. G. Shull	1994	Section 5.5.3, Section 10.2.2.4
1956	45 MWe energy production reactor in Calder Hallban	Great Britain		Chapter 7
1956-1965	Nucleogenesis: formation of elements in the universe	S. Chandrasekhar W. A. Fowler	1983	Section 6.2
1958	Discovery of the Mossbauer effect	R. Mossbauer	1961	Section 5.4.7
1959 1959	Radioimmunoassay (RIA): determination of peptide hormones The first civilian nuclear-powered ship (the Lenin icebreaker)	R. S. Yalow Soviet Union	1977	Section 12.3.1
1960	The first atomic bomb experiment by France	Algeria		Section 7.5
1960-1965 1961 1961	Classification of elementary particles Invention of 238Pu-powered satellite (Transit-4A) Semiconductor detectors	M. Gell-Mann	1969	Section 2.4 Section 14.3
1964	The first atomic bomb experiment by China	China		Section 7.5

Year	Discovery	Researcher(s)/county(ies)	Nobel In This Book Prize
1969	Plasma with high density in Tokamak fusion reactor	Soviet Union	Section 7.4
1974	The first atomic bomb experiment by India	India	Section 7.5
1974	Discovery of ancient natural nuclear reactor in Oklo (Gabon)	French scientists	Section 7.1.2
1976	SI-compatible-dose units (gray and sievert)	IUPAC	Section 13.4.1
1979	Accident at the Three Mile Island nuclear power plant	PA, USA	Section 7.2
1979?	The first atomic bomb experiment by Israel?		Section 7.5
1986	Accident at the Chernobyl nuclear power plant	Chernobyl, Soviet Union	Section 7.2
1998	The first atomic bomb experiment by Pakistan	Pakistan	Section 7.5
2006	The first atomic bomb experiment by North Korea	North Korea	Section 7.5
2011	Accident at the Fukushima nuclear power plant	Fukushima, Japan	Section 7.2

History of the Global Nuclear Power Industry

400 300

5 о

200 100 0

500

її “

300 200

о

Q.

100 0

In Table 1.1, the time of the experimental nuclear explosions by different countries is also mentioned. The useful applications of nuclear energy can be indicated by the increase in the capacity and number of nuclear power plants, as shown in Figure 1.1.

Further Reading

Becquerel, H. (1896). Sur les Radiations Invisibles Emises par les Corps Phosphorescents.

Comptes Rendus Acad. Sci. Paris 122:501—503.

Curie, M. (1898). Rayons Emis par les Composes de l’Uranium et du Thorium. Comptes Rendus Acad. Sci. Paris 126:1101 — 1103.

Curie, P. and Sklodowska-Curie, M. (1898). Sur une Nouvelle Substance Radioactive Contenu dans la Pechblende. Comptes Rendus Acad. Sci. Paris 127:175—178.

Vroman, R., 2003. List of states with nuclear weapons. < http:Zen. wikipedia. org/wiki/ List_of_states_with_nuclear_weapons.> (accessed 28.03.12.)

Trelvis, 2002. Nuclear power. < http://en. wikipedia. org/wiki/Nuclear_power.> (accessed 28.03.12.). Atomarchive. com, 1998—2011. < http://www. atomicarchive. com/Bios/Szilard. shtml.> (accessed 28.03.12.)

Hanh, O. (1962). Vom Radiothor zur Uranspalzung. Friedrich Vieweg & Sohn, Braunschweig. Haissinsky, M. (1964). Nuclear Chemistry and its Applications. Addison-Wesley, Reading, MA. Le Bon, G. (1912). L’evolution de la matiere. Flammarion, Paris.

Stein, W. (1958). Kulturfahrplan. F. A. Herbig Verlangbuchhandlung, Berlin.