Actinide vaporization

In summary, we have tried to describe the most recent state of understanding for the cohesive energies of the actinide metals. New results show there are still some surprises, even beyond the f-bonded early actinides. Vapor pressure measurements on Ra, Ac, and E are planned, along with completion of the Bk studies. The Pa and Pa-oxygen systems will obviously require extensive work. 

The criterion based on the vapor pressure holds for actinide Th and U, being non-volatile (their vapor pressures are much lower than La), were recently found to be encapsulated in a form of dicarbide, ThC2[25] and UC2[26], like lanthanide. 

Equilibrium vapor pressures were measured in this study by means of a mass spectrometer/target collection apparatus. Analysis of the temperature dependence of the pressure of each intermetallic yielded heats and entropies of sublimation. Combination of these measured values with corresponding parameters for sublimation of elemental Pu enabled calculation of thermodynamic properties of formation of each condensed phase. Previ ly reported results on the subornation of the PuRu phase and the Pu-Pt and Pu-Ru systems are correlated with current research on the PuOs and Pulr compounds. Thermodynamic properties determined for these Pu-intermetallics are compared to analogous parameters of other actinide compounds in order to establish bonding trends and to test theoretical predictions. 

Reliable data on the thermodynamic and phase relationships of actinide oxide systems are essential for reactor safety analysis. This paper reviews certain aspects of thermodynamic data currently available on the nonstoichiometric Pu-0 system, which may serve as a basis for use in reactor safety analysis. Emphasis is placed on phase relationships, vaporization behavior, oxygen-potential measurements, and evaluation of pertinent thermodynamic quantities. 

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. 

This article presents a general discussion of actinide metallurgy, including advanced methods such as levitation melting and chemical vapor-phase reactions. A section on purification of actinide metals by a variety of techniques is included. Finally, an element-by-element discussion is given of the most satisfactory metallurgical preparation for each individual element actinium (included for completeness even though not an actinide element), thorium, protactinium, uranium, neptunium, plutonium, americium, curium, berkelium, californium, and einsteinium. 

The vapor pressures at 1473 K of a few of the actinide elements and other materials of interest are given in Table III. All of the actinide (An) elements through einsteinium can be obtained by this process ... 

Fig. 1. Vapor pressures and some melting points of actinide metals Pa- Es. O, melting point.

The metallothermic reduction of an oxide is a useful preparative method for an actinide metal when macro quantities of the actinide are available. A mixture of the actinide oxide and reductant metal is heated in vacuum at a temperature which allows rapid vaporization of the actinide metal, leaving behind an oxide of the reductant metal and the excess reductant metal, in accord with the following equations ... 

The reductant metal must have the following properties (1) the free energy of formation of the oxide of the reductant has to be more negative than that of the actinide oxide and (2) the vapor pressure of the reductant metal needs to be smaller by several orders of magnitude than that of the actinide metal. This difference in vapor pressure should be at least five orders of magnitude to keep the contamination level of the co-evaporated reductant metal in the product actinide metal below the 10 ppm level. 

Actinide metals with lower vapor pressures (Th, Pa, and U) cannot be obtained by this method since no reductant metal exists which has a sufficiently low vapor pressure and a sufficiently negative free energy of formation of its oxide. For the large-scale production of U, Np, and Pu metals, the calciothermic reduction of the actinide oxide (Section II,A) followed by electrorefining of the metal product is preferred (24). In this process the oxide powder and solid calcium metal are vigorously stirred in a CaCl2 flux which dissolves the by-product CaO. Stirring is necessary to keep the reactants in intimate contact. 

The free energies of formation of the transition metal carbides are somewhat more negative than the free energies of formation of the actinide carbides. To facilitate separation of the actinide metal from the reaction products and excess transition metal reductant, a transition metal with the lowest possible vapor pressure is chosen as the reductant. Tantalum metal and tantalum carbide have vapor pressures which are low enough (at the necessary reaction temperature) to avoid contamination of the actinide metal by co-evaporation. 

In practice, a mixture of actinide dioxide and graphite powder is first pelletized and then heated to 2275 K in vacuum in a graphite crucible until a drop in the system pressure indicates the end of CO evolution. The resulting actinide carbide is then mixed with tantalum powder, and the mixture is pressed into pellets. The reduction occurs in a tantalum crucible under vacuum. At the reduction temperature, the actinide metal is vaporized and deposited on a tantalum or water-cooled copper condenser. 

The yield and rate of the tantalothermic reduction of plutonium carbide at 1975 K are given in Fig. 3. Producing actinide metals by metallothermic reduction of their carbides has some interesting advantages. The process is applicable in principle to all of the actinide metals, without exception, and at an acceptable purity level, even if quite impure starting material (waste) is used. High decontamination factors result from the selectivities achieved at the different steps of the process. Volatile oxides and metals are eliminated hy vaporization during the carboreduction. Lanthanides, Y, Ti, Zr, Hf, V, Nb, Ta, Mo, and W form stable carbides, whereas Rh, Os, Ir, Pt, and Pd remain as nonvolatile metals in the actinide carbides. Thus, these latter elements... 

This process is particularly useful for the preparation of pure plutonium metal from impure oxide starting material (111). It should also be applicable to the preparation of Cm metal. Common impurities such as Fe, Ni, Co, and Si have vapor pressures similar to those of Pu and Cm metals and are difficult to eliminate during the metallothermic reduction of the oxides and vaporization of the metals. They are eliminated, however, as volatile metals during preparation of the actinide carbides. 

The light actinide metals (Th, Pa, and U) have extremely low vapor pressures. Their preparation via the vapor phase of the metal requires temperatures as high as 2375 K for U and 2775 K for Th and Pa. Therefore, uranium is more commonly prepared by calciothermic reduction of the tetrafluoride or dioxide (Section II,A). Thorium and protactinium metals on the gram scale can be prepared and refined by the van Arkel-De Boer process, which is described next. 

Proceeding from thorium to plutonium along the actinide series, the vapor pressure of the corresponding iodides decreases and the thermal stability of the iodides increases. The melting point of U metal is below 1475 K and for Np and Pu metals it is below 975 K. The thermal stabilities of the iodides of U, Np, and Pu below the melting points of the respective metals are too great to permit the preparation of these metals by the van Arkel-De Boer process. 

Efficient refining of the more volatile actinide metals (Pu, Am, Cm, Bk, and Cf) is achieved by selective vaporization for those (Pu, Am, Cm) available in macro quantities. The metal is sublimed at the lowest possible temperature to avoid co-evaporation of the less volatile impurities and then deposited at the highest possible temperature to allow vaporization of the more volatile impurities. Deposition occurs below the melting point of the metal to avoid potential corrosion of the condenser by the liquid metal. Very good decontamination factors can be obtained for most metallic impurities. However, Ag, Ca, Be, Sn, Dy, and Ho are not separated from Am metal nor are Co, Fe, Cr, Ni, Si, Ge, Gd, Pr, Nd, Sc, Tb, and Lu from Cm and Pu metals. 

All subsequent preparations of Cf metal have used the method of choice, that is, reduction of californium oxide by La metal and deposition of the vaporized Cf metal (Section II,B) on a Ta collector 10, 30, 32, 45, 91, 97, 120). The apparatus used in this work is pictured schematically in Fig. 16. Complete analysis of Cf metal for cationic and anionic impurities has not been obtained due to the small (milligram) scale of the metal preparations to date. Since Cf is the element of highest atomic number available for measurement of its bulk properties in the metallic state, accurate measurement of its physical properties is important for predicting those of the still heavier actinides. Therefore, further studies of the metallic state of californium are necessary. 

Table XI gives the room-temperature, atmospheric pressure crystal structures, densities, and atomic volumes, along with the melting points and standard enthalpies of vaporization (cohesive energies), for the actinide metals. These particular physical properties have been chosen as those of concern to the preparative chemist who wishes to prepare an actinide metal and then characterize it via X-ray powder diffraction. The numerical values have been selected from the literature by the authors.

Actinide metal Crystal structure Density (g/cm ) Atomic volume (A ) Melting point (K) Enthalpy of vaporization AH, g (kJ/mol)... 

Sedimentation equilibrium technique, 19 256 Sedimentation velocity technique, 19 256 Sediments, arsenic in marine samples, 44 149, 162-164, 169, 181 [Se U ] cations, 35 297-298 Selective vaporization, for preparation of actinide metals, 31 12-13, 26 Selenide, production, 38 82 Selenium... 

Lanthanide and actinide complexes. Ln(L-L)) and An(L-L)4, of sterically hindered diketonates [e.g.. [Me3CC(0)CHC(0)CMej] fdpm) and [F CCF2CF2-CfOICHQOJCMeJ (fed)], are of considerable interest because of their volatility. Despite their high molecular weights, they have measurable vapor pressures at temperatures below the boiling point of water. This volatility has been exploited in... 

Curium trifluoride cun be reduced tn Ihc metal hy healing ill 275 C in a beryllia crucible wilh barium vapor. The metal is silvery in color and has the properties of an electropositive element in common wilh the other Actinide elements. 

The Absorption Spectra and Excited State Relaxation Properties of Lanthanide and Actinide Halide Vapor Complexes. I. ErCl3(AlCl3L, W.T. Camall, J.P. Hessler, H.R. Hoekstra, and C.W. Williams, J. Chem. Phys. 68, 4304-4309 (1978). 

Plutonium-noble metal compounds have both technological and theoretical importance. Modeling of nuclear fuel interactions with refractory containers and extension of alloy bonding theories to include actinides require accurate thermodynamic properties of these materials. Plutonium was shown to react with noble metals such as platinum, rhodium, iridium, ruthenium, and osmium to form highly stable intermetallics. Vapor pressures of phases in these systems were measured by the Knudsen effusion technique. Use of mass spectrometer-target collection apparatus to perform thermodynamic studies is discussed. The prominent sublimation reactions for these phases below 2000 K was shown to involve formation of elemental plutonium vapor. Thermodynamic properties determined in this study were correlated with corresponding values obtained from theoretical predictions and from previous measurements on analogous intermetallics. 

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