Rhenium elements

Noddack, Tacke, and Berg discover rhenium (element 75). 

After Niels Bohr s proposal of the atomic model and the reinterpretation of the periodic system by Moseley s rule, the search for the missing elements received a new impetus and numerous were the attempts to fill the last gaps in the periodic table. Several rare earths were isolated and, by 1924, only five elements were still to be discovered numbers 43, 61, 75, 85, and 87. Four of those elements are the natural radio-elements 43, 61, 85, and 87 and, for this reason, they escaped the searches led by chemists who were missing the right tool to isolate or even produce them in observable quantities. This was not the case with rhenium (element 75), the last stable element to be discovered and also one of the less abundant in the earth s crust. 

Technetium is a silvery-gray metal that tarnishes slowly in moist air. The common oxidation states of technetium are +7, +5, and +4. Under oxidizing conditions technetium (Vll) will exist as the pertechnetate ion, TcOr-. The chemistry of technetium is said to be similar to that of rhenium. Technetium dissolves in nitric acid, aqua regia, and cone, sulfuric acid, but is not soluble in hydrochloric acid of any strength. The element is a remarkable corrosion inhibitor for steel. The metal is an excellent superconductor at IIK and below. 

Tantalum is a gray, heavy, and very hard metal. When pure, it is ductile and can be drawn into fine wire, which is used as a filament for evaporating metals such as aluminum. Tantalum is almost completely immune to chemical attack at temperatures below ISOoC, and is attacked only by hydrofluoric acid, acidic solutions containing the fluoride ion, and free sulfur trioxide. Alkalis attack it only slowly. At high temperatures, tantalum becomes much more reactive. The element has a melting point exceeded only by tungsten and rhenium. Tantalum is used to make a variety... 

L. Rhenus, Rhine) Discovery of rhenium is generally attributed to Noddack, Tacke, and Berg, who announced in 1925 they had detected the element in platinum ore and columbite. They also found the element in gadolinite and molybdenite. By working up 660 kg of molybdenite in 1928 they were able to extract 1 g of rhenium. 

Rhenium hexafluoride is readily prepared by the direct interaction of purified elemental fluorine over hydrogen-reduced, 300 mesh (ca 48 pm) rhenium powder at 120°C. The reaction is exothermic and temperature rises rapidly. Failure to control the temperature may result in the formation of rhenium heptafluoride. The latter could be reduced to rhenium hexafluoride by heating with rhenium metal at 400°C. 

Rhenium heptafluoride [17029-21 -9], ReF, is obtained by the direct interaction of elemental fluorine with hydrogen-reduced rhenium powder at 400°C and slightly over atmospheric pressure of fluorine. It is a pale yeUow soHd, mol wt 319.19 mp, 48.3°C and bp, 73.7°C. 

Tungsten with the addition of as much as 5% thoria is used for thermionic emission cathode wires and as filaments for vibration-resistant incandescent lamps. Tungsten—rhenium alloys are employed as heating elements and thermocouples. Tantalum and niobium form continuous soHd solutions with tungsten. Iron and nickel are used as ahoy agents for specialized appHcations. 

Occurrence and Recovery. Rhenium is one of the least abundant of the naturally occurring elements. Various estimates of its abundance in Earth s cmst have been made. The most widely quoted figure is 0.027 atoms pet 10 atoms of silicon (0.05 ppm by wt) (3). However, this number, based on analyses for the most common rocks, ie, granites and basalts, has a high uncertainty. The abundance of rhenium in stony meteorites has been found to be approximately the same value. An average abundance in siderites is 0.5 ppm. In lunar materials, Re, when compared to Re, appears to be enriched by 1.4% to as much as 29%, relative to the terrestrial abundance. This may result from a nuclear reaction sequence beginning with neutron capture by tungsten-186, followed by p-decay of of a half-hfe of 24 h (4) (see Extraterrestrial materials). 

Occurrence of rhenium and molybdenum together in nature is a consequence of the similarities of these elements. Both elements have a high affinity for sulfide ion. Moreover, the radii of Re" " and Mo" ", 0.74 nm and 0.70 nm, respectively, ate almost identical, so that ReS2 [12038-63-0] and M0S2 have similar crystal stmctures with almost identical dimensions (see Molybdenumcompounds). 

Selected physical properties of rhenium are summarized ia Table 1. The metal is silvery-white and has a metallic luster. It has a high density (21.02 g/cm ). Only platinum, iridium, and osmium have higher densities. The melting poiat of rhenium is higher than that of all other elements except tungsten (mp 3410°C) and carbon (mp 3550°C). 

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. 

Salts of perrhenic acid may be obtained in acid—base reactions, and may include the tetrahedral ReO anion or the octahedral anion ReO , eg, in Ba (ReOg)2 [13598-09-9], Ammonium perrhenate and perrhenic acid, as well as rhenium metal, are sold by the primary suppHers of this element. 

Rhenium Halides and Halide Complexes. Rhenium reacts with chlorine at ca 600°C to produce rheniumpentachloride [39368-69-9], Re2Cl2Q, a volatile species that is dimeric via bridging hahde groups. Rhenium reacts with elemental bromine in a similar fashion, but the metal is unreactive toward iodine. The compounds ReCl, ReBr [36753-03-4], and Rel [59301-47-2] can be prepared by careful evaporation of a solution of HReO and HX. Substantiation in a modem laboratory would be desirable. Lower oxidation state hahdes (Re X ) are also prepared from the pentavalent or tetravalent compounds by thermal decomposition or chemical reduction. 

Ethylene oxide (qv) was once produced by the chlorohydrin process, but this process was slowly abandoned starting in 1937 when Union Carbide Corp. developed and commercialized the silver-catalyzed air oxidation of ethylene process patented in 1931 (67). Union Carbide Corp. is stiU. the world s largest ethylene oxide producer, but most other manufacturers Hcense either the Shell or Scientific Design process. Shell has the dominant patent position in ethylene oxide catalysts, which is the result of the development of highly effective methods of silver deposition on alumina (29), and the discovery of the importance of estabUshing precise parts per million levels of the higher alkaU metal elements on the catalyst surface (68). The most recent patents describe the addition of trace amounts of rhenium and various Group (VI) elements (69). 

Metals and alloys, the principal industrial metalhc catalysts, are found in periodic group TII, which are transition elements with almost-completed 3d, 4d, and 5d electronic orbits. According to theory, electrons from adsorbed molecules can fill the vacancies in the incomplete shells and thus make a chemical bond. What happens subsequently depends on the operating conditions. Platinum, palladium, and nickel form both hydrides and oxides they are effective in hydrogenation (vegetable oils) and oxidation (ammonia or sulfur dioxide). Alloys do not always have catalytic properties intermediate between those of the component metals, since the surface condition may be different from the bulk and catalysis is a function of the surface condition. Addition of some rhenium to Pt/AlgO permits the use of lower temperatures and slows the deactivation rate. The mechanism of catalysis by alloys is still controversial in many instances. 

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). 

However, like the mp, bp and enthalpy of atomization, it also reflects the weaker cohesive forces in the metallic lattice since for Tc and Re, which have much stronger metallic bonding, the -t-2 state is of little importance and the occurrence of cluster compounds with M-M bonds is a dominant feature of rhenium(III) chemistry. The almost uniform slope of the plot for Tc presages the facile interconversion between oxidation states, observed for this element. 

The first catalytic study of Reaction 1 was published in 1902 by Sabatier and Senderens (1) who reported that nickel was an excellent catalyst. Since that time, the active catalysts were identified as the transition elements with unfilled 3d, 4d, and 5d orbitals iron, cobalt, nickel, ruthenium, rhenium, palladium, osmium, indium, and platinum, as well as some elements that can assume these configurations (e.g., silver). These are discussed later. For practical operation of this process,... 

Rhenium isocyanide complex chemistry has not been nearly so extensively studied as that of other elements and so further efforts are obviously necessary. 

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