Actinide gaseous

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

THE ELECTRON CONFIGURATIONS OF GASEOUS ACTINIDE AND LANTHANIDE ATOMS... 

Isotope photoseparation techniques for actinides probably will include only gaseous systems, hexafluorides and metal vapors. Hence, aqueous actinide photochemistry is not likely to influence isotope separations. However, the intense interest in laser separation techniques for the gaseous systems promotes interest in the aqueous systems. 

The first S5m.thetic ventures into actinide and lanthanide organometalhc chemistry were attempted during World War II and were motivated by the need for stable, volatile uranium complexes in the uranium gaseous diffusion process. It soon became apparent that the homoalkyl complexes (MR4) of uranium were extremely unstable and at best could exist only as transient intermediates at low temperatures [128). With the isolation of the tricyclopentadienides of the lanthanides in 1954, the focus of /-transition metal organometaUic chemistry shifted to the n-carbocychc complexes and has remained unchanged until the recent isolation of stable alkyls and aryls of both the lanthanides and actinides. 

Two further points merit attention. PuPe is a very volatile substance, like the other actinide hexafluorides (mp 51.5 °C bp 62.15 °C) very reactive (it undergoes controlled hydrolysis to PUO2F2 and PUOF4), it tends to be decomposed by its own a-radiation, and is best kept in the gaseous state (resembling NO2 in appearance). 

The interaction of radiation with matter can have profound effects. Whether in solid, solution, or gaseous states, radioactivity can impact the environment and therefore change the molecular speciation of the actinides. To put this into perspective, three examples are discussed below plutonium metal, americium crystals, and an aqueous solution of plutonium. 

Table 14.3. Electron configuration of the actinides in the gaseous state.

Membrane technology may become essential if zero-discharge mills become a requirement or legislation on water use becomes very restrictive. The type of membrane fractionation required varies according to the use that is to be made of the treated water. This issue is addressed in Chapter 35, which describes the apphcation of membrane processes in the pulp and paper industry for treatment of the effluent generated. Chapter 36 focuses on the apphcation of membrane bioreactors in wastewater treatment. Chapter 37 describes the apphcations of hollow fiber contactors in membrane-assisted solvent extraction for the recovery of metallic pollutants. The apphcations of membrane contactors in the treatment of gaseous waste streams are presented in Chapter 38. Chapter 39 deals with an important development in the strip dispersion technique for actinide recovery/metal separation. Chapter 40 focuses on electrically enhanced membrane separation and catalysis. Chapter 41 contains important case studies on the treatment of effluent in the leather industry. The case studies cover the work carried out at pilot plant level with membrane bioreactors and reverse osmosis. Development in nanofiltration and a case study on the recovery of impurity-free sodium thiocyanate in the acrylic industry are described in Chapter 42. 

Additional research is required for each proposed process step so that accurate feasibility determinations can be made. The identity and quantity of the various actinide and fission-product species in the molten, solid, and gaseous phases are... 

Table 17. Summary of mass spectrometric studies of oxides of lanthanides or actinides and their quasi-binaries with transition metals except those listed in Table 18. (The gaseous species are underlined if their enthalpies of formation or of dissociation are given)... 

Semiempirical calculations of free energies and enthalpies of hydration derived from an electrostatic model of ions with a noble gas structure have been applied to the ter-valent actinide ions. A primary hydration number for the actinides was determined by correlating the experimental enthalpy data for plutonium(iii) with the model. The thermodynamic data for actinide metals and their oxides from thorium to curium has been assessed. The thermodynamic data for the substoicheiometric dioxides at high temperatures has been used to consider the relative stabilities of valence states lower than four and subsequently examine the stability requirements for the sesquioxides and monoxides. Sequential thermodynamic trends in the gaseous metals, monoxides, and dioxides were examined and compared with those of the lanthanides. A study of the rates of actinide oxidation-reduction reactions showed that, contrary to previous reports, the Marcus equation ... 

Figure 2. Comparison of gaseous entropies for the lanthanides and actinides at 298 K and 1400 K (V), Magnetic actinides (Y), nonmagnetic actinides (O), magnetic lanthanides nonmagnetic lanthanides (Q), low-lying levels removed,...

Some of the physical properties of metal tetrakis-boro-hydrides, which are primarily determined by their solid-state structure, are listed in Table 1. The polymeric Th, Pa, and U borohydrides are of much lower volatility than the monomeric Zr, Hf, Np, and Pu compounds. The intermolecular bonds connecting molecules together decrease their volatility substantially since these bonds break when the solid vaporizes (12). A plot of log p(mmHg) vs 1/T yields the equation log p(mmHg) = -A/T + B, where T is in K. Values of A and B allow the calculation of the heats (AH) and entropies (AS) for phase-change processes as shown in Table 1. The actinide ions in the polymeric compounds are 14 coordinate however, in the gaseous state they are 12 coordinate (12). 

This report is a comprehensive collection of the energy levels of the gaseous atoms and ions of all the actinide elements. The listing for Th(g) contains 693 energy levels, the highest level being at 46844 cm 2156 cm below the ionisation level, (49000 + 1000) cm . ... 

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