Probing local electronic and geometric changes of hydrated calcium vanadium oxide (CaxV2O5·yH2O) upon Zn ion intercalation
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ABSTRACT WD J204713.76–125908.9 is a new addition to the small class of white dwarfs with helium-dominated photospheres that exhibit strong Balmer absorption lines and atmospheric metal pollution. The exceptional abundances of hydrogen observed in these stars may be the result of accretion of water-rich rocky bodies. We obtained far-ultraviolet and optical spectroscopy of WD J204713.76–125908.9 using the Cosmic Origin Spectrograph on-board the Hubble Space Telescope and X-shooter on the Very Large Telescope, and identify photospheric absorption lines of nine metals: C, O, Mg, Si, P, S, Ca, Fe, and Ni. The abundance ratios are consistent with the steady-state accretion of exo-planetesimal debris rich in the volatile elements carbon and oxygen, and the transitional element sulphur, by factors of 17, 2, and 4, respectively, compared to the bulk Earth. The parent body has a composition akin to Solar system carbonaceous chondrites, and the inferred minimum mass, 1.6 × 1020 g, is comparable to an asteroid 23 km in radius. We model the composition of the disrupted parent body, finding from our simulations a median water mass fraction of 8 per cent.
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Crystal formation of pentasodium nonadecacesium tetracosatungstate(VI) heneikosahydrate, Na 5 Cs 19 [W 24 O 84 ]·21H 2 O, was successfully achieved by the conversion of [H 2 W 12 O 42 ] 10– through the addition of excess Cs + . The crystal structure comprising the toroidal isopolyoxidometalate is presented, as well as its Raman spectrum. Na 5 Cs 19 (H 2 O) 21 W 24 O 84 crystallizes in the rhombohedral space group R$\overline{3}$ with an obverse centering. The title compound represents the addition of a new member to the isopolytungstate family with mixed alkali counter-ions and contains rarely observed five-coordinate tungsten(VI) atoms in the [W 24 O 84 ] 24– anion (site symmetry C 3i ) arising from the conversion mediated by Cs + counter-ions.
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Achieving high temperature lifts (>200 K) via a chemical heat pump based on salt hydration/dehydration reactions requires the transport of water vapor from low to high pressure. Alternative compression approaches require condensing of low-pressure water vapor, pumping of liquid water, and subsequent evaporation when the low-side pressure corresponds to sub-ambient water saturation temperatures. Thus, this study compares four steam compression methods for use within a chemical heat pump system based on a reversible calcium oxide hydration/dehydration reaction with a temperature lift from 350 °C heat to >600 °C. Purely mechanical and thermochemical/mechanical compression technologies are considered. A parametric study of maximum allowable temperature, the isentropic efficiency of mechanical compressors, the effectiveness of heat exchangers, and the assumed allowable heat exchanger pressure drop is conducted to determine the mechanical and thermal energy consumed per kilogram of compressed steam. The system complexity in terms of the number of main system components, maximum pressure ratio, and maximum allowable temperature is estimated. Model results show an absorption-based steam compressor has the highest exergetic efficiency for the required chemical heat pump required conditions. As a result, this system configuration was then experimentally demonstrated to illustrate the impact of system performance on component effectiveness.
Exchange of oxygen stable isotopes (δ 18 O values) between precipitation waters and uranium oxides is governed by thermodynamics or kinetics. It has been assumed that meteoric waters can be related to precipitation waters in uranium ore concentrates and their calcination and reduced uranium oxide products. With this assumption, the δ 18 O values of uranium materials could provide forensic signatures that identify the production history and geolocation of nuclear materials. To further exploit the potential of δ 18 O values in nuclear material analysis, this study examines the oxygen stable isotope exchange in two UOCs, magnesium diuranate (MDU) and sodium diuranate (SDU). MDU and SDU were synthesized from solutions of uranyl nitrate hexahydrate using precipitation waters with unique oxygen isotope compositions. The structures of the MDU and SDU were analyzed using powder X-ray diffraction (p-XRD) and thermal mass loss curves, while the δ 18 O values of waters generated during thermal decomposition were analyzed using a thermogravimetric analyzer coupled to an isotope ratio infrared spectrometer (TGA-IRIS). By p-XRD, the MDU was uniform and amorphous across all syntheses with residual crystalline material incorporated as a minor component. Combined with the TGA results, all of the MDU is likely amorphous MgU 2 O 7 ·3H 2 O with MgO impurities present throughout. In contrast, the SDU synthesis resulted in multiple phases with many samples exhibiting crystalline phases including a combination of Na(UO 2 ) 4 O 2 (OH) 5 ·5H 2 O and Na 2 (UO2) 6 O 4 (OH) 6 ·8H 2 O with a Na 2 U 2 O 7 minor phase. A small fraction of the SDU samples were amorphous with no crystalline XRD peaks observed. Mass loss curves of the SDU samples revealed that the amorphous samples contained inclusions of similar crystalline phases compared to the crystalline materials. The uniformity of the MDU samples enabled highly reproducible measurements of δ 18 O values of the water vapor yielded for two dehydration events at 170 °C and 500 °C. In contrast, the multiphase composition of the SDU samples resulted in poor reproducibility in δ 18 O values. In conclusion, neither system revealed any correlation between the δ 18 O values of precipitation water, and the waters released during dehydration of the UOCs.