Elements actinides

Actinide Elements.- Complexes of general structure (n-C5H R)M(solv)jjCl3 (R = H, Me M = Th, U solv = THF, MeCN x = 

3) have been obtained from MCI, by chloride-displacement 63  

Chisholm and R. K. Potkul, Synth. React. Inorg. Metal-Org. Chem., 1978, 8, 65. 

Studies of General Intm est.— The electron distributions in Cr(CO) -( -PhH)Cr(CO)3, and ( -PhH)2Cr have been estimated from analysis of photoelectron spectra. Factors affecting the relative reactivities towards nucleophilic addition (of PR3) of cationic ( -hydrocarbon)M(CO)3 complexes, including [(7 -PhH)Mn(CO)8]+, have been discussed.  

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Tracer studies using 253Es show that einsteinium has chemical properties typical of a heavy trivalent, actinide element. 

Experiments seem to show that the element possesses a moderately stable dipositive (11) oxidation state in addition to the tripositive (111) oxidation state, which is characteristic of the actinide elements. 

The actinide elements are a group of chemically similar elements with atomic numbers 89 through 103 and their names, symbols, atomic numbers, and discoverers are given in Table 1 (1-3) (see Thorium and thorium compounds Uranium and uranium compounds Plutonium and plutonium compounds Nuclear reactors and Radioisotopes). 

Each of the elements has a number of isotopes (2,4), all radioactive and some of which can be obtained in isotopicaHy pure form. More than 200 in number and mosdy synthetic in origin, they are produced by neutron or charged-particle induced transmutations (2,4). The known radioactive isotopes are distributed among the 15 elements approximately as follows actinium and thorium, 25 each protactinium, 20 uranium, neptunium, plutonium, americium, curium, californium, einsteinium, and fermium, 15 each herkelium, mendelevium, nobehum, and lawrencium, 10 each. There is frequently a need for values to be assigned for the atomic weights of the actinide elements. Any precise experimental work would require a value for the isotope or isotopic mixture being used, but where there is a purely formal demand for atomic weights, mass numbers that are chosen on the basis of half-life and availabiUty have customarily been used. A Hst of these is provided in Table 1. 

Ion exchange (qv see also Chromatography) is an important procedure for the separation and chemical identification of curium and higher elements. This technique is selective and rapid and has been the key to the discovery of the transcurium elements, in that the elution order and approximate peak position for the undiscovered elements were predicted with considerable confidence (9). Thus the first experimental observation of the chemical behavior of a new actinide element has often been its ion-exchange behavior—an observation coincident with its identification. Further exploration of the chemistry of the element often depended on the production of larger amounts by this method. Solvent extraction is another useful method for separating and purifying actinide elements. 

Ion-exchange separations can also be made by the use of a polymer with exchangeable anions in this case, the lanthanide or actinide elements must be initially present as complex ions (11,12). The anion-exchange resins Dowex-1 (a copolymer of styrene and divinylben2ene with quaternary ammonium groups) and Amherlite IRA-400 (a quaternary ammonium polystyrene) have been used successfully. The order of elution is often the reverse of that from cationic-exchange resins. 

Isotopes sufficiently long-Hved for work in weighable amounts are obtainable, at least in principle, for all of the actinide elements through fermium (100) these isotopes with their half-Hves are Hsted in Table 2 (4). Not all of these are available as individual isotopes. It appears that it will always be necessary to study the elements above fermium by means of the tracer technique (except for some very special experiments) because only isotopes with short half-Hves are known. 

Special techniques for experimentation with the actinide elements other than Th and U have been devised because of the potential health ha2ard to the experimenter and the small amounts available (15). In addition, iavestigations are frequently carried out with the substance present ia very low coaceatratioa as a radioactive tracer. Such procedures coatiaue to be used to some exteat with the heaviest actinide elements, where only a few score atoms may be available they were used ia the earHest work for all the transuranium elements. Tracer studies offer a method for obtaining knowledge of oxidation states, formation of complex ions, and the solubiHty of various compounds. These techniques are not appHcable to crystallography, metallurgy, and spectroscopic studies. 

Microchemical or ultramicrochemical techniques are used extensively ia chemical studies of actinide elements (16). If extremely small volumes are used, microgram or lesser quantities of material can give relatively high concentrations in solution. Balances of sufficient sensitivity have been developed for quantitative measurements with these minute quantities of material. Since the amounts of material involved are too small to be seen with the unaided eye, the actual chemical work is usually done on the mechanical stage of a microscope, where all of the essential apparatus is in view. Compounds prepared on such a small scale are often identified by x-ray crystallographic methods. 

Table 3. Electronic Configurations for Gaseous Atoms of Lanthanide and Actinide Elements...

The close chemical lesemblance among many of the actinide elements permits their chemistry to be described for the most part in a correlative way... 

The actinide elements exhibit uniformity in ionic types. In acidic aqueous solution, there are four types of cations, and these and their colors are hsted in Table 5 (12—14,17). The open spaces indicate that the corresponding oxidation states do not exist in aqueous solution. The wide variety of colors exhibited by actinide ions is characteristic of transition series of elements. In general, protactinium(V) polymerizes and precipitates readily in aqueous solution and it seems unlikely that ionic forms ate present in such solutions. 

The reduction potentials for the actinide elements ate shown in Figure 5 (12—14,17,20). These ate formal potentials, defined as the measured potentials corrected to unit concentration of the substances entering into the reactions they ate based on the hydrogen-ion-hydrogen couple taken as zero volts no corrections ate made for activity coefficients. The measured potentials were estabhshed by cell, equihbrium, and heat of reaction determinations. The potentials for acid solution were generally measured in 1 Af perchloric acid and for alkaline solution in 1 Af sodium hydroxide. Estimated values ate given in parentheses. 

Thousands of compounds of the actinide elements have been prepared, and the properties of some of the important binary compounds are summarized in Table 8 (13,17,18,22). The binary compounds with carbon, boron, nitrogen, siUcon, and sulfur are not included these are of interest, however, because of their stabiUty at high temperatures. A large number of ternary compounds, including numerous oxyhaUdes, and more compHcated compounds have been synthesized and characterized. These include many intermediate (nonstoichiometric) oxides, and besides the nitrates, sulfates, peroxides, and carbonates, compounds such as phosphates, arsenates, cyanides, cyanates, thiocyanates, selenocyanates, sulfites, selenates, selenites, teUurates, tellurites, selenides, and teUurides. 

F. L. Getting, M. H. Rand, and R. J. Ackermaim, ia F. L. Oettiag, ed.. The Chemical Thermodynamics of Actinide Elements and Compounds, Part 1, The Actinide Elements, SHlPDBj424j 1, IAEA, Vienna, Austria, 1976. 

Thorium [7440-29-1], a naturally occurring radioactive element, atomic number 90, atomic mass 232.0381, is the second element of the actinide ( f) series (see Actinides AND transactinides Radioisotopes). Discovered in 1828 in a Norwegian mineral, thorium was first isolated in its oxide form. For the light actinide elements in the first half of the. series, there is a small energy difference between and 5/ 6d7 electronic configurations. Atomic spectra... 

There is no single best form of the periodic table since the choice depends on the purpose for which the table is used. Some forms emphasize chemical relations and valence, whereas others stress the electronic configuration of the elements or the dependence of the periods on the shells and subshells of the atomic structure. The most convenient form for our purpose is the so-called long form with separate panels for the lanthanide and actinide elements (see inside front cover). There has been a lively debate during the past decade as to the best numbering system to be used for the individual... 

The remaining actinide elements were prepared by various bombardment techniques fairly regularly over the next 25 years (Table 31.1) though, for reasons of national security, publication of the results was sometimes delayed. The dominant figure in this field has been G. T. Seaborg, of the University of California, Berkeley, in early recognition of which, he and E. M. McMillan were awarded the 1951 Nobel Prize for Chemistry. 

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