Technetium discovery

Gr. technetos, artificial) Element 43 was predicted on the basis of the periodic table, and was erroneously reported as having been discovered in 1925, at which time it was named masurium. The element was actually discovered by Perrier and Segre in Italy in 1937. It was found in a sample of molybdenum, which was bombarded by deuterons in the Berkeley cyclotron, and which E. Eawrence sent to these investigators. Technetium was the first element to be produced artificially. Since its discovery, searches for the element in terrestrial material have been made. Finally in 1962, technetium-99 was isolated and identified in African pitchblende (a uranium rich ore) in extremely minute quantities as a spontaneous fission product of uranium-238 by B.T. Kenna and P.K. Kuroda. If it does exist, the concentration must be very small. Technetium has been found in the spectrum of S-, M-, and N-type stars, and its presence in stellar matter is leading to new theories of the production of heavy elements in the stars. 

Plutonium was the first element to be synthesized in weighable amounts (6,7). Technetium, discovered in 1937, was not isolated until 1946 and not named until 1947 (8). Since the discovery of plutonium in 1940, production has increased from submicrogram to metric ton quantities. Because of its great importance, more is known about plutonium and its chemistry than is known about many of the more common elements. The metallurgy and chemistry are complex. MetaUic plutonium exhibits seven aUotropic modifications. Five different oxidation states are known to exist in compounds and in solution. 

The isolation and identification of 4 radioactive elements in minute amounts took place at the turn of the century, and in each case the insight provided by the periodic classification into the predicted chemical properties of these elements proved invaluable. Marie Curie identified polonium in 1898 and, later in the same year working with Pierre Curie, isolated radium. Actinium followed in 1899 (A. Debierne) and the heaviest noble gas, radon, in 1900 (F. E. Dorn). Details will be found in later chapters which also recount the discoveries made in the present century of protactinium (O. Hahn and Lise Meitner, 1917), hafnium (D. Coster and G. von Hevesey, 1923), rhenium (W. Noddack, Ida Tacke and O. Berg, 1925), technetium (C. Perrier and E. Segre, 1937), francium (Marguerite Percy, 1939) and promethium (J. A. Marinsky, L. E. Glendenin and C. D. Coryell, 1945). 

Elements 43 (technetium), 61 (promethium), 85 (astatine), and all elements with Z > 92 do not exist naturally on the Earth, because no isotopes of these elements are stable. After the discovery of nuclear reactions early in the twentieth century, scientists set out to make these missing elements. Between 1937 and 1945, the gaps were filled and three actinides, neptunium (Z = 93), plutonium (Z = 94), and americium (Z = 95) also were made. 

The discovery of the elements 43 and 75 was reported by Noddack et al. in 1925, just seventy years ago. Although the presence of the element 75, rhenium, was confirmed later, the element 43, masurium, as they named it, could not be extracted from naturally occurring minerals. However, in the cyclotron-irradiated molybdenum deflector, Perrier and Segre found radioactivity ascribed to the element 43. This discovery in 1937 was established firmly on the basis of its chemical properties which were expected from the position between manganese and rhenium in the periodic table. However, ten years later in 1937, the new element was named technetium as the first artificially made element. 

Progress in understanding stellar evolution and nucleosynthesis, and the discovery by Merrill (1952) of the unstable element technetium in the S star R Andromedae, demonstrating the occurrence of stellar nucleosynthesis within a few half-lives of Tc (i.e. < about 1 Myr see Fig. 1.8), has led to acceptance of the idea that abundance variations among stars are perfectly natural as a consequence of three main effects (see Fig. 3.37) ... 

Almost all of the elements heavier than He are synthesized in the interiors of stars. The work of Burbidge et al. (1957) gives the theoretical framework for the synthesis of the elements. The experimental evidence of active nucleosynthesis came from the discovery of the unstable nuclei of technetium in the spectra of red giants (Merrill 1952). The solar elemental and isotopic abundances which are taken from the primitive carbonaceous chondrites constitute the guidelines for testing such models (Anders and Grevesse 1989). A minimum of eight basic processes are required to reproduce the observed compositions. Nucleosynthetic... 

Existence of technetium was predicted from the vacant position in the Periodic Table between manganese and rhenium. Noddack, Tacke, and Berg reported its discovery in 1925 and named it masurium. The metal actually was never isolated from any source by these workers. Its existence, therefore, could not be confirmed. Perrier and Segre in 1937 produced this element by bombarding molybdenum metal with deuterons in a cyclotron. They named the element technetium derived from the Greek word technetos, meaning artificial. 

TECHNETIUM. [CAS 7440-26-8J. Chemical element symbol Tc, at. no. 43, at. wt. 98.906, penodic table group 7, mp 2l 72 ">C, bp 4877 TT, does not occur in nature. The present location of technetium in die penodic table was vacant for many years, during which time several claims to having found the element were made, but never confirmed. One such claimant termed the element masurium. Technetium has been detected in certain stars and this discovery mnst be resolved with current theories of stellar evolution and element synthesis. 

It is only in recent times that a polemic arose about the naming of element 43. See P. H. M. Van Assche, The ignored discovery of element Z=43, Nuclear Physics A480 (1988) 205-214 and G. Herrmann, Technetium or masurium - a comment on the history of element 43, Nuclear Physics A505 (1989) 352-360. 

Due to these recent discoveries, chemists did not lose their faith and they still hoped to discover the element 61 in nature. But most of them realized that it would probably be more successful to synthesize the element artificially. Technetium, the first artificially prepared element, had been formed in 1937 in the Berkeley cyclotron (Perrier and Segre, 1937,1947). One year later, in July 1938, the American physicists Pool and Quill of the University of Ohio started bombarding a neodymium target with fast deuterons (Pool and Quill, 1938). They were hoping that the proton would be taken up by the neodymium nuclei, with the formation of element 61 as a consequence ... 

The development of the instant radiopharmaceutical kit in the 1970s was followed by the development of technetium imaging agents for renal, skeletal, and hepatobiliary imaging. At that time, the coordination chemistry of technetium was not well understood and as a result, the early radiopharmaceuticals are not fully characterized. Studies of the coordination chemistry of technetium intensified in the late 1970s leading to the discovery of Tc brain, heart, and renal agents. These... 

KroU H (1952) The participation of heavy metal ions in the hydrolysis of amino acid esters. J Am Chem Soc 74 2036-2039 Kruck T, Lang A (1997) Ober MetaU-Trifluorphosphin-Komplexe. XV. Tris-(trifluorphosphin-nitrosyleisenhydrid. Chemische Berichte 99 3794-3799 Kuroda PK (1998) A note on the discovery of technetium. Nucl Phys A503 178-182... 

The discovery of technetium (Z = 43) in 1937 and of promethium (Z = 61) in 1947 filled the two gaps in the Periodic Table of the elements. These gaps had been the reason for many investigations. Application of Mattauch s rule (section 2.3) leads to the conclusion that stable isotopes of element 43 cannot exist. Neighbouring stable isotopes could only be expected for mass numbers A 93, A < 91, A = 103 and A > 105. However, these nuclides are relatively far away from the line of jd stability. The report by Noddak and Tacke concerning the discovery of the elements rhenium and masurium (1925) was only correct with respect to Re (Z = 75). The concentration of element 43 (Tc) in nature due to spontaneous or neutron-induced fission of uranium is several orders of magnitude too low to be detectable by emission of characteristic X rays of element 43, as had been claimed in the report. 

I don t say that they should change from basic research to applied research they still may be carrying on the basic research, but they need to explain to the public the importance of it. So many things are discovered. For example, in the case of my discovery of all these radioactive isotopes — technetium-99m, iodine-131, cobalt-60, and cesium-137, all turned out to have tremendous practical applications in nuclear medicine. There are millions of applications per year now. 

When a discovery like this is announced, other chemists try to repeat the experiments. They see if they get the same results as those reported. In this case, the German team turned out to be half right. Scientists were able to confirm the existence of element 75. They were not able to confirm the Germans discovery of element 43. In fact, it was another decade before element 43 (technetium) was actually discovered. 

Volumes 3-6 describe developments in the coordination chemistry of the metallic elements since 1982 (x, p, and /-block metals, transition metals of Groups 3-6 7-8 9-12). These volumes correspond to Volumes 3, 4, and 5 in CCC. A review of technetium coordination chemistry was unavailable when CCC was published, and a complete account of its development from the earliest discoveries to present-day applications is incorporated in the new work. In these volumes space limitations restrict the material that can be presented. The information that appears has been selected to give a near comprehensive coverage of new discoveries, new interpretations of experiment and theory, and applications, where relevant. 

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