The persistence of many seemingly metastable mineral assemblages in sediments and soils is commonly attributed to their sluggish transformation to the stable-phase assemblage. Although undoubtedly kinetics plays a major role, this study shows that thermodynamic factors, particularly surface energy, significantly influence the free energy. Enthalpies of formation of boehmite samples with variable surface area were derived using high-temperature oxide-melt calorimetry. The average surface enthalpy for all faces terminating boehmite particles was calculated at +0.52 ± 0.12 J/m2. This value represents the surface enthalpy for surfaces exposed to vacuum assuming that H2O adsorbed on the surface of boehmite is loosely bound. These results show that the enthalpy of formation of boehmite may vary by ≤8 kJ/mol as a function of particle size. An overview of published values of surface energies of gibbsite, γ-Al2O3, corundum, and the results here indicates that the hydrated phases (boehmite, gibbsite) have lower surface energies than the anhydrous phases (corundum, γ-Al2O3). Lower surface energies allow the hydrated phases to maintain high surface area, i.e., small particle size. Similar surface energies of boehmite and gibbsite suggest kinetic control favoring the crystallization of boehmite or gibbsite from aqueous solution. The enthalpy of formation of bulk boehmite from the elements was calculated at −994.0 ±1.1 kJ/mol. Combining this result with the data in existing thermodynamic databases, we confirm that bulk boehmite is metastable with respect to bulk diaspore at ambient conditions.

The formation of mixed-metal-Al layered double hydroxide (LDH) phases similar to hydrotalcite has been identified as a significant mechanism for immobilization of trace metals in some environmental systems. These precipitate phases become increasingly stable as they age, and their formation may therefore be an important pathway for sequestration of toxic metals in contaminated soils. However, the lack of thermodynamic data for LDH phases makes it difficult to model their behavior in natural systems. In this work, enthalpies of formation for Ni LDH phases with nitrate and sulfate interlayers were determined and compared to recently published data on carbonate interlayer LDHs. Differences in the identity of the anion interlayer resulted in substantial changes in the enthalpies of formation of the LDH phases, in the order of increasing enthalpy carbonate<sulfate<nitrate. Substitution of silica for carbonate resulted in an even more exothermic enthalpy of formation, confirming that silica substitution increases the stability of LDH precipitates. Both mechanical mixture and solid-solution models could be used to predict the thermodynamic properties of the LDH phases. Modeling results based on these thermodynamic data indicated that the formation of LDH phases on soil mineral substrates decreased Ni solubility compared to Ni(OH)2 over pH 5–9 when soluble Al is present in the soil substrate. Over time, both of these precipitate phases will transform to more stable Ni phyllosilicates.

High-temperature oxide-melt solution calorimetry and acid-solution calorimetry were used to determine the heat of dissolution of synthetic goethite with particle sizes in the range 2–75 nm and measured surface areas of 30–273 m2/g (27–240 × 103 m2/mol). Sample characterization was performed using X-ray diffraction, Fourier transform infrared spectroscopy, the Brunauer, Emmett and Teller method and thermogravimetric analysis. Water content (structural plus excess water) was determined from weight loss after firing at 1100°C. Calorimetric data were corrected for excess water assuming this loosely adsorbed water has the same energetics as bulk liquid water. The enthalpy of formation was calculated from calorimetric data using enthalpies of formation of hematite and liquid water as reference phases for high-temperature oxide-melt calorimetry and using enthalpy of formation of lepidocrocite for acid-solution calorimetry. The enthalpy of formation of goethite can vary by 15–20 kJ/mol as a function of surface area. The plot of calorimetric data vs. surface area gives a surface enthalpy of 0.60±0.10 J/m2 and enthalpy of formation of goethite (with nominal composition FeOOH and surface area = 0) of −561.5±1.5 kJ/mol. This surface enthalpy of goethite, which is lower than values reported previously, clarifies previous inconsistencies between goethite-hematite equilibrium thermodynamics and observations in natural systems.

Interest in hydrotalcite-like compounds has grown due to their role in controlling the mobility of aqueous metals in the environment as well as their use as catalysts, catalyst precursors and specialty chemicals. Although these materials have been studied in a number of contexts, little is known of their thermodynamic properties. High-temperature oxide melt solution calorimetry was used to measure the standard enthalpy of formation for compounds M(II)1−xAlx(OH)2(CO3)x/2·mH2O (0.2 < x < 0.4, M(II) = Mg, Co, Ni and Zn). The enthalpy of formation of these compounds from the relevant single cation phases was also determined. The formation of HTLCs results in a 5–20 kJ/mol enthalpy stabilization from the single cation hydroxides and carbonates and water. The data are correlated to two variables: the ratio of divalent to trivalent cation in the solid (M(II)/Al) and the identity of the divalent cation. It was observed that the M(II)/Al ratio exerts a minor influence on the enthalpy of formation from single-cation phases, while greater differences in stabilization resulted from changes in the chemical nature of the divalent cation. However, the data do not support any statistically significant correlation between the composition of HTLCs and their heats of formation. Equilibrium geochemical calculations based upon the thermodynamic data illustrate the effect of HTLCs on the speciation of metals in natural waters. These calculations show that, in many cases, HTLCs form even in waters that are undersaturated with respect to the individual divalent metal hydroxides and carbonates. Phase diagrams and stability diagrams involving Ni-bearing HTLCs and the single-cation components are presented. The Ni(II) concentration as a function of pH as well as the stability diagram for the equilibrium among minerals in the CaO-NiO-Al2O3-SiO2-CO2-H2O system at 298 K are plotted.

Feroxyhyte (δ′-FeOOH) is a relatively uncommon Fe oxide mineral and one of the few phases in the system Fe2O3-H2O for which thermodynamic properties are not known. In natural occurrences, it is always fine-grained, although samples with larger particle sizes and better crystallinity (labeled as δ-FeOOH) can be prepared in the laboratory. This contribution presents a thermochemical study on a series of feroxyhyte samples. One is fine-grained and poorly crystalline, similar to natural materials, while the other three are of better crystallinity. The enthalpy of formation of feroxyhyte at 298.15 K is −547.4±1.3kJ mol−1 for the poorly crystalline sample (surface area 88 m2/g), and −550.6±1.4, −550.9±1.3, and −552.6±1.2 kJ mol−1 for the samples with better crystallinity. The entropy of feroxyhyte can be estimated only crudely, because it is influenced to a great extent by its magnetic properties, particle size, and structural disorder. The $S_{298}^{\text{o}}$$S_{298}^{\rm{o}}$ of feroxyhyte is estimated here to be 65±5 J K−1 mol−1. The Gibbs free energy of the reaction feroxyhyte → hematite + liquid water is −7.4 to −12.6 kJ mol−1 at 298.15 K. The Gibbs free energy of formation ($\text{Δ}{G}_{\text{f}}^{\text{o}}$${\rm{\Delta }}G_{\rm{f}}^{\rm{o}}$) of the fine-grained, poorly crystalline feroxyhyte is −478.1±2.0 kJ mol−1 at 298.15 K. Since this sample is closest in its physical properties to natural feroxyhyte, this $\text{Δ}{G}_{\text{f}}^{\text{o}}$${\rm{\Delta }}G_{\rm{f}}^{\rm{o}}$ value should be used in thermodynamic modeling related to processes involving naturally occurring feroxyhyte. In terms of Gibbs free energy and enthalpy, feroxyhyte is very similar to lepidocrocite and maghemite, and, like these two phases, has no thermodynamic stability field in the system Fe2O3-H2O, except possibly at the nanoscale.

Understanding the thermodynamic stability of materials plays an essential role in their applications. The high-temperature oxide melt solution calorimetry is a reliable method developed to experimentally measure formation enthalpy. Until now, it has been mostly used for the characterization of oxide materials. We introduce modifications in the experimental technique which makes it suitable for a wide range of non-oxide compounds. The modified methodology was used to measure the heat effects associated with the oxidative dissolution of almost all p-elements of groups III, IV, V, and VI and verified by calculating the standard enthalpies of formation of the corresponding oxides at 298 K. The results presented serve as a compelling database for pure p-elements, which will provide a very straightforward way of calculating the formation enthalpies of non-oxide systems based on high-temperature calorimetric experiments.

Carbonate glasses can be formed routinely in the system K2CO3–MgCO3. The enthalpy of formation for one such 0.55K2CO3–0.45MgCO3 glass was determined at 298 K to be 115.00 ± 1.21 kJ/mol by drop solution calorimetry in molten sodium molybdate (3Na2O·MoO3) at 975 K. The corresponding heat of formation from oxides at 298 K was −261.12 ± 3.02 kJ/mol. This ternary glass is shown to be slightly metastable with respect to binary crystalline components (K2CO3 and MgCO3) and may be further stabilized by entropy terms arising from cation disorder and carbonate group distortions. This high degree of disorder is confirmed by 13C MAS NMR measurement of the average chemical shift tensor values, which show asymmetry of the carbonate anion to be significantly larger than previously reported values. Molecular dynamics simulations show that the structure of this carbonate glass reflects the strong interaction between the oxygen atoms in distorted carbonate anions and potassium cations.

Enthalpies of formation and heat capacities are key parameters for thermodynamic assessments using the CALPHAD method and were determined in this work in the ZrO2–Y0.5Ta0.5O2 quasibinary system. ZrxY0.5−x/2Ta0.5−x/2O2 samples with compositions in the monoclinic and tetragonal ZrO2-based solid solutions (0.65 ≤ x ≤ 1) as well as the two monoclinic (M′ and M) polymorphs of the Y0.5Ta0.5O2-based solid solutions (0 ≤ x ≤ 0.2) were investigated. The enthalpies of the two monoclinic polymorphs M′ and M are essentially the same within experimental uncertainty and have significant energetic stability (enthalpies of formation near −45 kJ/mol) relative to their component oxides. The monoclinic and tetragonal zirconia-rich solid solutions have little energetic stability with respect to ZrO2, Ta2O5, and Y2O3 and presumably owe their existence to the configurational entropy. The heat capacities of M′ and M phase are similar and can be estimated from their constituent oxides using the Neumann–Kopp rule.

The BaNd2O4 compound and the BaO–Nd2O3 system are of interest for electroceramics. In this work, we synthesized BaNd2O4 by solid-state reaction, measured its heat capacity from 573 to 1273 K by differential scanning calorimetry, and determined its enthalpy of formation from component oxides at 298 K by high-temperature oxide melt solution calorimetry to be −43.75 ± 4.68 kJ/mol. Our newly determined values and available literature data were employed to assess the phase equilibria in the BaO–Nd2O3 system using CALPHAD methodology. A self-consistent thermodynamic database and the calculated phase diagram of the BaO–Nd2O3 system are provided. The optimized thermodynamic parameters are in good agreement with available experimental data. BaNd2O4 is calculated to melt incongruently at 2177 K. This thermodynamic analysis is essential for the optimization of synthesis conditions for materials and for the evaluation of their stability under appropriate technological operating conditions.

The thermodynamic properties of ZnxMn3−xO4 and Mg1−zCuzCr2O4 spinel solid solutions have been studied using high-temperature oxide melt solution calorimetry. Except for MgCr2O4 spinel, which possesses cubic structure, the other three end-members are tetragonal. The enthalpies of mixing are small endothermic and fit subregular solution behavior. The main contribution to the energetics of mixing of both spinel systems comes from the difference in the crystal structure between the end-members: a change in the tetragonal distortion for ZnxMn3−xO4 solid solutions and a transition from cubic to tetragonal for the Mg1−zCuzCr2O4 system. If all Mg1−zCuzCr2O4 spinels possessed the same structure, the mixing enthalpies would be close to zero. Because both series have normal cation distributions, the entropies of mixing are equal to the configurational entropies of mixing of Zn2+ and Mn2+ and of Mg2+ and Cu2+ on tetrahedral sites, and the activities would follow Raoult’s law. The calculated Gibbs energy of mixing confirms the absence of solvus at any temperature for both systems.

Enthalpies of water adsorption on amorphous and crystalline oxides and peroxides of uranium are reported. Despite substantial structural and computational research on reactions between actinides and water, understanding their surface interactions from the energetic perspective remains incomplete. Direct calorimetric measurements of hydration energetics of nano-sized, bulk-sized UO2, U3O8, anhydrous γ-UO3, amorphous UO3, and U2O7 were carried out, and their integral adsorption enthalpies were determined to be −67.0, −70.2, −73.0, −84.1, −61.6, and −83.6 kJ/mol water, with corresponding water coverages of 4.6, 4.5, 4.1, 5.2, 4.4, and 4.1 H2O per nm2, respectively. These energetic constraints are important for understanding the interfacial phenomena between water and U-containing phases. Additionally, this set of data also helps predict the absorption and desorption behavior of water from nuclear waste forms or used nuclear fuels under repository conditions. There are also underlying relations for water coverage among different U compounds. These experimentally determined data can be used as benchmark values for future computational investigations.

Surface water can affect the properties of metal oxide nanoparticles. Investigations on several systems revealed that nanoparticles have different thermodynamic properties than their bulk counterparts due to adsorbed water on their surfaces. Some thermodynamically metastable phases of bulk metal oxides become stable when reduced to the nanoscale, partially due to interactions between high energy surfaces and surface water. Water adsorption microcalorimetry and high-temperature oxide melt solution calorimetry, low-temperature specific heat calorimetry, and inelastic neutron scattering are used to understand the interactions of surface water with metal oxide nanoparticles. Computational methods, such as molecular dynamics simulations and density functional theory calculations, have been used to study these interactions. Investigations on titania, cassiterite, and alumina illustrate the insights gained by these measurements. The energetics of water on metal oxide surfaces are different from those of either liquid water or hexagonal ice, and there is substantial variation in water interactions on different metal oxide surfaces.

Nanoparticles are ubiquitous in both natural and synthetic environments, providing much of the chemical reactivity for geochemical, planetary, environmental, and technological processes. However, this reactivity and differences between the bulk and nanoscale are thermodynamically, as well as kinetically, controlled. Energetic effects arising from differences in surface energies of different nanomaterials lead to changes in which phases are thermodynamically stable under given conditions. This results in crossovers in polymorphic stability as a function of particle size and substantial shifts in the positions of dehydration and redox equilibria. Examples of these phenomena in aluminum, cobalt, iron, and manganese oxides are presented, and implications for catalysts, battery materials, and other functional oxides are discussed. A hypothesis is presented that low surface energy and the resulting relatively weak water binding on the surface leads to better function when electrons or ions are transferred at the solid-solution interface.

The rare earth (RE) mineral loparite with the chemical composition (RE, Na, Sr, Ca)(Ti, Nb, Ta, Fe+3)O3 is the principal ore of the light rare earth elements (LREE) as well as niobium and tantalum. The enthalpies of formation of RE0.67-xNa3xTiO3 (RE = La, Ce) and Ca1-2xNaxLaxTiO3 from oxides and elements of lanthanum and cerium perovskites and their solid solutions have been obtained using high temperature oxide melt solution calorimetry. RE0.67-xNa3xTiO3 (RE = La, Ce) perovskites become more stable relative to oxide components as sodium content increases. Na0.5Ce0.5TiO3 and Na0.5La0.5TiO3 can be considered stable endmembers in natural loparite minerals. For perovskite solid solutions Ca1-2xNaxLaxTiO3, the enthalpies of formation from the constituent oxides $\Delta {\rm{H}}_{{\rm{f}},\,{\rm{ox}}}^^\circ$ become more exothermic with increasing Na+La content, suggesting a stabilizing effect of the substitution 2Ca2+ → Na+ + La3+ on the perovskite structure. The trend of increasing thermodynamic stability with decreasing structural distortion is similar to that seen in many other ABO3 perovskites.

In the present work, for the first time, the inorganic Si-based materials lacking preexisting mixed bonds (O–Si–C, silicon in tetrahedral coordination bonded to both carbon and oxygen) have been successfully used as starting materials in a laser evaporation/condensation system for making hydrogenated silicon oxycarbide (Si–O–C–H) nanoparticles containing mixed bonds. The obtained materials are characterized by spectroscopic, microscopic, and calorimetric measurements. Thermodynamically stable 5–10 nm amorphous Si–O–C–H particles with a complex structure containing a combination of pure and mixed Si-based tetrahedral units (SiOiC4−i; i = 0–4), and a considerable amount of Si–OH and C–H bonds have been synthesized. The nanoparticles possess high surface areas (428–467 m2/g), suggesting potential use in functionalities requiring high surface to volume ratios. In addition, making thermodynamically stable Si–O–C–H ceramics using a pathway different from the polymer route raises the likelihood of formation of similar carbon containing compounds in the planetary accretion and the Earth's interior.

The surface enthalpy of yttria-stabilized hafnia (YSH) (YxHf1 − xO2 − x/2) with different compositions was directly measured by a combination of high-temperature oxide-melt solution calorimetry and water adsorption calorimetry. The surface enthalpies for hydrated surfaces are 0.27 ± 0.06 J/m2 for x = 0.1, 0.77 ± 0.09 J/m2 for x = 0.17, and 1.30 ± 0.09 J/m2 for x = 0.24; and those for anhydrous surfaces are 0.51 ± 0.06, 1.08 ± 0.13, and 1.76 ± 0.09 J/m2 respectively. The enthalpies of both hydrated and anhydrous surfaces increase approximately linearly (R2 > 0.93) with increasing yttrium concentration. The surface enthalpies of Y0.1Hf0.9O1.95 were used to approximate those for pure anhydrous cubic hafnia. Combining the data relating to surface energies for monoclinic hafnia from our previous work and estimated data for tetragonal hafnia, a tentative stability map of HfO2 polymorphs as a function of surface area (SA) was constructed.