Gas-phase isothermal chromatogaphy is a method by which volatile compounds of different chemical elements can be separated according to their volatilities. The technique, coupled with theoretical modeling of the processes occurring in the chromatogaphy column, provides accurate determination of thermodynamic properties (e.g., adsorption enthalpies) for compounds of elements, such as the transactinides, which can only be produced on an atom-at-a-time basis. In addition, the chemical selectivity of the isothermal chromatogaphy technique provides the decontamination from interfering activities necessary for the determination of the nuclear decay properties of isotopes of the transactinide elements. Volatility measurements were performed on chloride species of Rf and its group 4 homologs, Zr and Hf, as well as Ha and its group 5 homologs, Nb and Ta. Adsorption enthalpies were calculated for all species using a Monte Carlo code simulation based on a microscopic model for gas thermochromatography in open columns with laminar flow of the carrier gas. Preliminary results are presented for Zr- and Nb-bromides
The chemical and nuclear properties of Lr and Ha have been studied, using 3-minute 260 Lr and 35-second 262 Ha. The crystal ionic radius of Lr 3+ was determined by comparing its elution position from a cation-exchange resin column with those of lanthanide elements having known ionic radii. Comparisons are made to the ionic radii of the heavy actinides, Am 3+ through Es 3+ , obtained by x-ray diffraction methods, and to Md 3+ and Fm 3+ which were determined in the same manner as Lr 3+ . The hydration enthalpy of -3622 kJ/mol was calculated from the crystal ionic radius using an empirical form of the Born equation. Comparisons to the spacings between the ionic radii of the heaviest members of the lanthanide series show that the 2Z spacing between Lr 3+ and Md 3+ is anomalously small, as the ionic radius of Lr 3+ of 0.0886 nm is significantly smaller than had been expected. The chemical properties of Ha were determined relative to the lighter homologs in group 5, Nb and Ta. Group 4 and group 5 tracer activities, as well as Ha, were absorbed onto glass surfaces as a first step toward the determination of the chemical properties of Ha. Ha was found to adsorb on surfaces, a chemical property unique to the group 5 elements, and as such demonstrates that Ha has the chemical properties of a group 5 element. A solvent extraction procedure was adapted for use as a micro-scale chemical procedure to examine whether or not Ha displays eka-Ta-like chemical under conditions where Ta will be extracted into the organic phase and Nb will not. Under the conditions of this experiment Ha did not extract, and does not show eka-Ta-like chemical properties
Pershina, V.; Fricke, B.; Ionova, G.V.; Johnson, E.
The basic thermodynamic functions, the entropy, free energy, and enthalpy, for element 105 (hahnium) in electronic configurations d 3 s 2 , d 3 sp, and d 4 s 1 and for its + 5 ionized state (5f 14 ) have been calculated as a function of temperature. The data are based on the results of the calculations of the corresponding electronic states of element 105 using the multiconfiguration Dirac-Fock method. 19 refs., 1 fig., 11 tabs
Ionova, G.V.; Pershina, V.; Johnson, E.; Fricke, B.; Schaedel, M.
Standard redox potentials Edeg(M z+x /M z+ ) in acidic solutions for group 5 elements including element 105 (Ha) and the actinide, Pa, have been estimated on the basis of the ionization potentials calculated via the multiconfiguration Dirac-Fock method. Stability of the pentavalent state was shown to increase along the group from V to Ha, while that of the tetra- and trivalent states decreases in this direction. Our estimates have shown no extra stability of the trivalent state of hahnium. Element 105 should form mixed-valence complexes by analogy with Nb due to the similar values of their potentials Edeg(M 3+ /M 2+ ). The stability of the maximum oxidation state of the elements decreases in the direction 103 > 104 > 105. (orig.)
Studies of the chemical properties of the elements at the uppermost end of the periodic table are discussed. Some historical perspective is given, but major emphasis is on recent studies. Isotopes of these elements are short-lived and, therefore, must be studied near the site of production. They must be produced with charged-particle beams at accelerators rather than via neutron capture. The use of radioactive heavy actinide targets is often required and the number of atoms produced is so small that any chemistry to be performed must be done on an ''atom-at-a-time'' basis. Furthermore, a knowledge of their nuclear properties is required in order to identify and detect them. To date, both gas and aqueous phase properties of elements as heavy as element 104 (rutherfordium) and element 105 (hahnium) have been investigated, even though their longest-lived known isotopes have half-lives of only 65 and 35 seconds, respectively. The experimental results show that their chemical properties cannot be simply extrapolated from the known properties of their lighter homologs in the periodic table, emphasizing the importance of obtaining additional experimental information for the heaviest elements to compare with predictions and help assess the influence of relativistic effects. The feasibility of the extension of chemical studies to still heavier elements is also discussed. (orig.)