Enthalpies of formation of lanthanide oxyapatite phases

A family of lanthanide silicates adopts an oxyapatite-like structure with structural formula Ln9.33∎0.67(SiO4)6O2 (Ln 4 La, Sm, Nd, Gd, ∎ = vacancy). The enthalpies of solution, DHS, for these materials and their corresponding binary oxides were determined by high-temperature oxide melt solution calorimetry using molten 2PbO·B2O3 at 1078 K. These data were used to complete thermodynamic cycles to calculate enthalpies of formation from the oxides, ΔHs f-oxides (kJ/mol): La9.33∎0.67(SiO4)6O2 = −776.3 ± 17.9, Nd9.33∎0.67(SiO4)6O2 = −760.4 ± 31.9, Sm9.33∎0.67(SiO4)6O2 = −590.3 ± 18.6, and Gd9.33∎0.67(SiO4)6O2 = −446.9 ± 21.9. Reference data were used to calculate the standard enthalpies of formation from the elements, ΔH0 f (kJ/mol): La9.33∎0.67(SiO4)6O2 = −14611.0 ± 19.4, Nd9.33∎0.67(SiO4)6O2 = −14661.5 ± 32.2, Sm9.33∎0.67(SiO4)6O2 = −14561.7 ± 20.8, and Gd9.33∎0.67(SiO4)6O2 = −14402.7 ± 28.2. The formation enthalpies become more endothermic as the ionic radius of the lanthanide ion decreases

Grain Growth-Controlled Giant Permittivity in Soft Chemistry CaCu3Ti4O12 Ceramics

We report a dielectric constant of up to 5.4105 at room temperature and 1 kHz for CaCu3Ti4O12 (CCTO) ceramics, derived from multiphase powders (coprecipitation products), made by a ‘‘chimie douce’’ (coprecipitation) method, and then sintered in air. The sintered products are pure-phase CCTO ceramics. The high dielectric constant is achieved by tuning the size of grains and the thickness of grain boundaries. The grain growth is controlled by varying the concentration of excess CuO in the initial powder (calcined coprecipitation products) between 1 and 3.1 wt%. The dielectric constant of pure CCTO ceramics increases with the initial CuO concentration, reaching its maximum at 2.4 wt% of CuO. A further increase of excess CuO in powders results in a permittivity decrease, accompanied by the formation of CuO as a separate phase in the sintered products. The unusual grain growth behavior is attributed to a eutectic reaction between CuO and TiO2 present in the initial powder

Synthesis, characterization and thermochemistry of synthetic Pb–As, Pb–Cu and Pb–Zn jarosites

The enthalpy of formation from the elements of well characterized Pb-As, Pb-Cu, and Pb-Zn synthetic jarosites, corresponding to chemical formulas (H3O)0.68±0.03Pb0.32±0.002Fe2.86±0.14(SO4)1.69±0.08(AsO4)0.31±0.02(OH)5.59±0.28(H2O)0.41±0.02, (H3O)0.67±0.03Pb0.33±0.02Fe2.71±0.14Cu0.25±0.01(SO4)2±0.00(OH)5.96±0.30(H2O)0.04±0.002 and (H3O)0.57±0.03Pb0.43±0.02Fe2.70±0.14Zn0.21±0.01(SO4)2±0.00(OH)5.95±0.30(H2O)0.05±0.002, was measured by high temperature oxide melt solution calorimetry and gave ΔH°f = -3691.2 ± 8.6 kJ/mol, ΔH°f = -3653.6 ± 8.2 kJ/mol, and ΔH°f = -3669.4 ± 8.4 kJ/mol, respectively. Using estimated entropies, the standard Gibbs free energy of formation from elements at 298 K ΔG°f of the three compounds were calculated to be -3164.8 ± 9.1 kJ/mol, -3131.4 ± 8.7 kJ/mol, and -3153.6 ± 8.9 kJ/mol, respectively. Based on these free energies, their logKsp values are -13.94 ± 1.89, -4.38 ± 1.81 and -3.75 ± 1.80, respectively. For this compounds, a log10{Pb2+} - pH diagram is presented. The diagram shows that the formation of Pb-As jarosite may decrease aqueous arsenic and lead concentrations to meet drinking water standards. The new thermodynamic data confirm that transformation of Pb-As jarosite to plumbojarosite is thermodynamically possible

Tunable Low Density Palladium Nanowire Foams

Nanostructured palladium foams offer exciting potential for applications in diverse fields such as catalyst, fuel cell, and particularly hydrogen storage technologies. We have fabricated palladium nanowire foams using a cross-linking and freeze-drying technique. These foams have a tunable density down to 0.1% of the bulk, and a surface area to volume ratio of up to 1,540,000:1. They exhibit highly attractive characteristics for hydrogen storage, in terms of loading capacity, rate of absorption and heat of absorption. The hydrogen absorption/desorption process is hysteretic in nature, accompanied by substantial lattice expansion/contraction as the foam converts between Pd and PdHx.Comment: 17 pages, 4 figure

Thermochemistry of a New Class of Materials Containing Dinitrogen Pairs in an Oxide Matrix

International audienceA series of N 2 -containing perovskite phases was prepared in the La-(Ba)-Ti-O system in order to study the dinitrogen retention phenomenon from a thermochemical viewpoint. High-temperature oxide melt solution calorimetry was undertaken to determine the energetics of the corresponding startingoxynitrides, intermediate phases, and oxides. Calorimetric results show that nitrogen is weakly bound within the oxide matrix and most of the enthalpy of oxidation of the intermediate phase is devoted to its structure change between the starting perovskite structure and the formation of a layered-perovskiteLa2Ti2O7 oxide

Energetics of nanoparticle oxides: interplay between surface energy and polymorphism†

Many oxides tend to form different structures (polymorphs) for small particles. High temperature oxide melt solution calorimetry has been used to measure the enthalpy as a function of polymorphism and surface area for oxides of Al, Ti, and Zr. The results confirm crossovers in polymorph stability at the nanoscale. The energies of internal and external surfaces of zeolitic silicas with open framework structures are an order of magnitude smaller than those of oxides of normal density

Heat capacities of TiO2-bearing silicate liquids: Evidence for anomalous changes in configurational entropy with temperature

The heat capacities of several TiO2-bearing silicate glasses and liquids containing Cs2O, Rb2O, Na2O, K2O, CaO, MgO, or BaO have been measured to 1100 K using a differential scanning calorimeter and to 1800 K using a Setaram HT-1500 calorimeter in step-scanning mode. The results for liquids of M2O-TiO2-2SiO2 composition (M -- Na, K, Cs) are compared to those for liquids of M2O-3SiO2 composition. The presence of TiO2 has a profound influence on the heat capacity of simple three-component silicate liquids over the temperature range 900-1300 K. Specifically, replacement of Si4+ by Ti4+ leads to doubling of the magnitude of the jump in Cp at the glass transion (Tg); this is followed by a progressive decrease in liquid Cp for over 400 K, until Cp eventually becomes constant and similar to that in Ti-free systems. The large heat capacity step at Tg in the TiO2-bearing melts suggests significant configurational rearrangements in the liquid that are not available to TiO2-free silicates. In addition, these "extra" configurational changes apparently saturate as temperature increases, implying the completion of whatever process is responsible for them, or the attainment of a random distribution of structural states. Above 1400 K, however, where the heat capacities of TiO2-bearing and TiO2-free alkali silicate liquids are similar, their configurational entropies differ by ~3.5 J/g.f.w.-K. The larger configurational entropy of the TiO2-bearing alkali silicate liquids relative to the TiO2-free liquids is energetically equivalent to raising the liquid temperature by more than 300 degrees. This result clearly demonstrates the energetic magnitude of the configurational changes apparent in the supercooled liquid region and their impact on the thermodynamic properties of the stable liquid. Consideration of both density measurements on liquids and spectroscopic data on quenched glasses (from the literature) suggests that the anomalous configurational rearrangements may involve the breakdown of alkali and alkaline earth titanate complexes and changes in Ti4+ coordination.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/30728/1/0000377.pd

Steam-Induced Coarsening of Single-Unit-Cell MFI Zeolite Nanosheets and Its Effect on External Surface Brønsted Acid Catalysis.

Commonly used methods to assess crystallinity, micro-/mesoporosity, Brønsted acid site density and distribution (in micro- vs. mesopores), and catalytic activity suggest nearly invariant structure and function for aluminosilicate zeolite MFI two-dimensional nanosheets before and after superheated steam treatment. Yet, pronounced reaction rate decrease for benzyl alcohol alkylation with mesitylene, a reaction that cannot take place in the zeolite micropores, is observed. Transmission electron microscopy images reveal pronounced changes in nanosheet thickness, aspect ratio and roughness indicating that nanosheet coarsening and the associated changes in the external (mesoporous) surface structure are responsible for the changes in the external surface catalytic activity. Superheated steam treatment of hierarchical zeolites can be used to alter nanosheet morphology and regulate external surface catalytic activity while preserving micro- and mesoporosity, and micropore reaction rates

Characterization of structural changes in modern and archaeological burnt bone: Implications for differential preservation bias

Structural and thermodynamic factors which may influence burnt bone survivorship in archaeological contexts have not been fully described. A highly controlled experimental reference collection of fresh, modern bone burned in temperature increments 100–1200˚C is presented here to document the changes to bone tissue relevant to preservation using Fourier transform infrared spectroscopy and X-ray diffraction. Specific parameters investigated here include the rate of organic loss, amount of bone mineral recrystallization, and average growth in bone mineral crystallite size. An archaeological faunal assemblage ca. 30,000 years ago from Tolbor-17 (Mongolia) is additionally considered to confirm visibility of changes seen in the modern reference sample and to relate structural changes to commonly used zooarchaeological scales of burning intensity. The timing of our results indicates that the loss of organic components in both modern and archaeological bone burnt to temperatures up to 700˚C are not accompanied by growth changes in the average crystallite size of bone mineral bioapatite, leaving the small and reactive bioapatite crystals of charred and carbonized bone exposed to diagenetic agents in depositional contexts. For bones burnt to temperatures of 700˚C and above, two major increases in average crystallite size are noted which effectively decrease the available surface area of bone mineral crystals, decreasing reactivity and offering greater thermodynamic stability despite the mechanical fragility of calcined bone. We discuss the archaeological implications of these observations within the context of Tolbor-17 and the challenges of identifying anthropogenic fire