Technetium properties

Physical Properties. Molybdenum has many unique properties, leading to its importance as a refractory metal (see Refractories). Molybdenum, atomic no. 42, is in Group 6 (VIB) of the Periodic Table between chromium and tungsten vertically and niobium and technetium horizontally. It has a silvery gray appearance. The most stable valence states are +6, +4, and 0 lower, less stable valence states are +5, +3, and +2. 

As a general rule, elements in the second and third transition series have similar chemical properties. In contrast, the properties of the first member of the series are often different. This pattern of behavior is seen in Group 7 (VIIB). The properties of rhenium and technetium differ considerably from those of manganese. 

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). 

Some of the important properties of Group 7 elements are summarized in Table 24.1. Technetium is an artificial element, so its atomic weight depends on which isotope has been produced. The atomic weights of Mn and Re, however, are known with considerable accuracy. In the case of... 

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. 

Although there are a lot of publications on the chemistry of technetium [2-4] and transition-metal clusters [1,5-8], the chemistry of technetium clusters was insufficiently studied until the early eighties [1,2]. Nevertheless, the available scanty data on the compounds with Tc-Tc bonds inspired hope that interesting results would be obtained in the chemistry of technetium in general, in radiochemistry, and in the chemistry of transition-metal cluster compounds. The anticipated results were actually obtained [9-15] and the conclusion was drawn that technetium had a number of anomalous cluster-forming properties [9]. This review looks at the detailed studies of these properties and their interpretation in terms of electronic structure theory. 

It should be noted that the above classification system of technetium cluster compounds is not the only possible one. In section 4 another classification is described, which is based on thermal stability and the mechanism of thermal decomposition. Section 2.2 is concerned with the classification based on methods of synthesizing cluster compounds. The classifications based on specific properties of clusters do not at all belittle the advantages of the basic structural classification they broaden the field of application of the latter, because for a better understanding and explanation of any chemical, physico-chemical and physical properties it is necessary to deal directly or indirectly with the molecular and/or electronic structures of the clusters. 

Table 2. Appearances and main properties of polynuclear bromide technetium clusters [11, 44, 53, 72, 76]...

In addition to research on the structure and other physicochemical properties in the solid state and solution, research into the thermal stability of technetium... 

Because magnetic, spectroscopic and other physicochemical properties of technetium clusters have been discussed in detail in our earlier reviews [9-15,77,103, 108,113,127-129], primary attention is given in this paper to a discussion of the electronic structure of technetium acido-clusters. 

Thus, the investigations performed [58,77] showed that [Tc2(/t-CH3COO)4] [TCO4J2 combines the properties of two classes of technetium complexes those of pertechnetates and those of binuclear carboxylates with multiple M-M bonds. On the other hand, the anionic and cationic fragments of this compound are characterized by a mutual effect which affects their electronic and molecular structures. 

The long-wavelength IR spectra of trigonal prismatic technetium clusters and a number of unusual physico-chemical properties of the clusters with ferrieinium cations [108] support the latter assumption. The discovered properties of the clusters with ferrieinium cations may be accounted for by the formation of the conductivity bands and, probably, hard-fermion bands in these compounds by the 5s(5p)-AO s of technetium atoms and 4s(4p)-AO s of the iron atoms. The formation of these bands may be supported by the following facts the ESR spectra of these compounds with geft close to that of a free electron temperature independent conductivity and an unusual temperature dependence of the Mossbauer and X-ray photoelectron spectra [108]. 

HOMO-LUMO. This may be supported by low Zeff of technetium atoms in tetragonal-prismatic clusters [103,127] and formation of compounds with fer-ricinium cations with some unusual physico-chemical properties, as is the case of trigonal-prismatic clusters [108,128]. 

In closing, recovery of technetium from waste solution should be touched upon. Studies of the base hydrolysis of technetium P-diketone complexes revealed that all of the complexes studied decompose in an alkaline solution even at room temperature, until technetium is finally oxidized to pertechnetate. These phenomena are very important for the management of technetium in waste solutions. Since most metal ions precipitate in alkaline solution, only technetium and some amphoteric metal ions can be present in the filtrate [29]. A further favorable property of pertechnetate is its high distribution coefficient to anion exchangers. Consequently, it is possible to concentrate and separate technetium with anion exchangers from a large volume of waste solution this is especially effective using an alkaline solution [54],... 

Gerlit, J.B. Some chemical properties of Technetium. Peaceful uses of... 

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