Density functional studies of the structural characteristics, Al NMR chemical shifts and water-exchange reactions of Al30O8(OH)56(H2O)26(Al30) in aqueous solution

In this paper, the structure of the Al₃₀O₈(OH)₅₆(H₂O)₂₆¹⁸⁺(Al₃₀) polyoxocation in aqueous solution is investigated, including an exploration of its water-exchange reaction using a supramolecular model. Thirty-one solvent water molecules were explicitly included in the supramolecular model to approximate the influence of the solvent. The calculated results indicated that both the gas-phase and the supramolecular models could correctly reproduce the structure of the Al₃₀ polyoxocation, but the supramolecular model described the structure more accurately. Using the supramolecular model, we calculated the ²⁷Al NMR chemical shifts of various aluminum atoms using HF and GIAO methods, and they compared well to the chemical shifts determined experimentally. The water-exchange reaction of the Al₃₀ polyoxocation could not be simulated with the gas phase model because of a proton-transfer reaction that is induced by the highly positive charge of the Al₃₀ polyoxocation. However, the inclusion of an explicit second solvation sphere lowered the acidity of the coordinated water molecules and allowed simulation of the water exchange reaction.     

Rates of oxygen exchange between the Al2O8Al28(OH)56(H2O)26(aq) (Al30) molecule and aqueous solution

Rates of steady exchange of oxygens between bulk solution and the largest known aluminum polyoxocation: Al₂O₈Al₂₈(OH)₅₆(H₂O)₂₆¹⁸⁺(aq) (Al₃₀) are reported at pH≈4.7 and 32-40°C. The Al₃₀ molecule is a useful model for geochemists because it is ≈2 nm in length, comparable to the smallest colloidal solids, and it has structural complexity greater than the surfaces of most aluminum (hydr)oxide minerals. The Al₃₀ molecule has 15 distinct hydroxyl sites and eight symmetrically distinct bound waters. Among the hydroxyl bridges are two sets of μ₃-OH, which are not present in any of the other aluminum polyoxocations that have yet been studied by NMR methods. Rates of isotopic equilibration of the μ₂-OH and μ₃-OH hydroxyls and bound water molecules fall within the same range as we have determined for other aluminum solutes, although it is impossible to determine rate laws for exchange at the large number of individual oxygen sites. After injection of ¹⁷O-enriched water, growth of the ¹⁷O-NMR peak near 37 ppm, which is assigned to μ₂-OH and μ₃-OH hydroxyl bridges, indicates that these bridges equilibrate within two weeks at temperatures near 35°C. The peak at +22 ppm in the ¹⁷O-NMR spectra, assigned to bound water molecules (η-OH₂), varies in width with temperature in a similar fashion as for other aluminum solutes, suggesting that most of the η-OH₂ sites exchange with bulk solution at rates that fall within the range observed for other aluminum complexes. Signal from one anomalous group of four η-OH₂ sites is not observed, indicating that these sites exchange at least a factor of ten more rapidly than the other η-OH₂ sites on the Al₃₀.     

The kinetics of oxygen exchange between the GeO4Al12(OH)24(OH2)12(aq) molecule and aqueous solutions

We report rates of oxygen exchange with bulk solution for an aqueous complex, ^IVGeO₄Al₁₂(OH)₂₄(OH₂)₁₂⁸⁺(aq) (GeAl₁₂), that is similar in structure to both the ^IVAlO₄Al₁₂(OH)₂₄(OH₂)₁₂⁷⁺(aq) (Al₁₃) and ^IVGaO₄Al₁₂(OH)₂₄(OH₂)₁₂⁷⁺(aq) (GaAl₁₂) molecules studied previously. All of these molecules have ε-Keggin-like structures, but in the GeAl₁₂ molecule, occupancy of the central tetrahedral metal site by Ge(IV) results in a molecular charge of +8, rather than +7, as in the Al₁₃ and GaAl₁₂. Rates of exchange between oxygen sites in this molecule and bulk solution were measured over a temperature range of 274.5 to 289.5 K and 2.95 < pH < 4.58 using ¹⁷O-NMR.Apparent rate parameters for exchange of the bound water molecules (η-OH₂) are k_ex²⁹⁸ = 200 (±100) s⁻¹, ΔH^‡ = 46 (±8) kJ · mol⁻¹, and ΔS^‡ = −46 (±24) J · mol⁻¹ K⁻¹ and are similar to those we measured previously for the GaAl₁₂ and Al₁₃ complexes. In contrast to the Al₁₃ and GaAl₁₂ molecules, we observe a small but significant pH dependence on rates of solvolysis that is not yet fully constrained and that indicates a contribution from the partly deprotonated GeAl₁₂ species.The two topologically distinct μ₂-OH sites in the GeAl₁₂ molecule exchange at greatly differing rates. The more labile set of μ₂-OH sites in the GeAl₁₂ molecule exchange at a rate that is faster than can be measured by the ¹⁷O-NMR isotopic-equilibration technique. The second set of μ₂-OH sites have rate parameters of k_ex²⁹⁸ = 6.6 (±0.2) · 10⁻⁴ s⁻¹, ΔH^‡ = 82 (±2) kJ · mol⁻¹, and ΔS^‡ = −29 (±7) J · mol⁻¹ · K⁻¹, corresponding to exchanges ≈40 and ≈1550 times, respectively, more rapid than the less labile μ₂-OH sites in the Al₁₃ and GaAl₁₂ molecules. We find evidence of nearly first-order pH dependence on the rate of exchange of this μ₂-OH site with bulk solution for the GeAl₁₂ molecule, which contrasts with Al₁₃ and GaAl₁₂ molecules.     

Residence times for protons bound to three oxygen sites in the AlO4Al12(OH)24(H2O)12 polyoxocation

Although, the kinetic reactivity of a mineral surface is determined, in part, by the rates of exchange of surface-bound oxygens and protons with bulk solution, there are no elementary rate data for minerals. However, such kinetic measurements can be made on dissolved polynuclear clusters, and here we report lifetimes for protons bound to three oxygen sites on the AlO₄Al₁₂(OH)₂₄(H₂O)₁₂⁷⁺ (Al₁₃) molecule, which is a model for aluminum-hydroxide solids in water. Proton lifetimes were measured using ¹H NMR at pH ∼ 5 in both aqueous and mixed solvents. The ¹H NMR peak for protons on bound waters (η-H₂O) lies near 8 ppm in a 2.5:1 mixture of H₂O/acetone-d₆ and broadens over the temperature range −20 to −5 °C. Extrapolated to 298 K, the lifetime of a proton on a η-H₂O is τ²⁹⁸ ∼ 0.0002 s, which is surprisingly close to the lifetime of an oxygen in the η-H₂O (∼0.0009 s), but in the same general range as lifetimes for protons on fully protonated monomer ions of trivalent metals (e.g., Al(H₂O)₆³⁺). The lifetime is reduced somewhat by acid addition, indicating that there is a contribution from the partly deprotonated Al₁₃ molecule in addition to the fully protonated Al₁₃ at self-buffered pH conditions. Proton lifetimes on the two distinct sets of hydroxyls bridging two Al(III) (μ₂-OH) differ substantially and are much shorter than the lifetime of an oxygen at these sites. The average lifetimes for hydroxyl protons were measured in a 2:1 mixture of H₂O/dmso-d₆ over the temperature range 3.7-95.2 °C. The lifetime of a hydrogen on one of the μ₂-OH was also measured in D₂O. The τ²⁹⁸ values are ∼0.013 and ∼0.2 s in the H₂O/dmso-d₆ solution and the τ²⁹⁸ value for the μ₂-OH detectable in D₂O is τ²⁹⁸ ∼ 0.013 s. The ¹H NMR peak for the more reactive μ₂-OH broadens slightly with acid addition, indicating a contribution from an exchange pathway that involves a proton or hydronium ion. These data indicate that surface protons on minerals will equilibrate with near-surface waters on the diffusional time scale.     

Activation volumes for oxygen exchange between the GaO4Al12(OH)24(H2O)127+(aq) (GaAl12) polyoxocation and aqueous solution from variable pressure O NMR spectroscopy

Activation volumes for exchange of oxygen between bulk aqueous solution and sites in the GaO₄Al₁₂(OH)₂₄(H₂O)₁₂⁷⁺(aq) (GaAl₁₂) complex were measured by variable-pressure ¹⁷O NMR techniques. Near 322 K, rates of exchange for the less labile set of bridging hydroxyls in the GaAl₁₂ decrease by a factor of about two with increasing pressure from 0.1 to 350 MPa. These data indicate a substantially positive activation volume of ΔV^‡ = +7 ± 1 cm³/mol, which is the first activation volume measured for a bridging hydroxyl in a polynuclear complex. This result suggests significant bond-lengthening in the activation step. Electrostriction effects should be small because exchange occurs via a pH-independent path under the experimental conditions. The second, more labile set of bridging hydroxyls exchange too rapidly for the variable-pressure techniques employed here. The exchange of bound-water molecules on the GaAl₁₂ was observed at P = 350 MPa using the ¹⁷O-NMR line-broadening technique. Comparison with previous measurements at 0.1 MPa indicates decreasing line width from 0.1 to 350 MPa for temperatures at which exchange dominates, yielding an activation volume of ΔV^‡ = +3(± 1) cm³/mol. This activation volume is smaller than the value for the Al(H₂O)₆³⁺ complex, suggesting that water exchange on the larger GaAl₁₂ complex has less dissociative character although the average charge density is lower.     

Free energy of formation for green rust sodium sulphate (NaFe6Fe3(OH)18(SO4)2(s))

In a recent study, sulphate-bearing green rust (GR_SO4) was shown to incorporate Na⁺ in its structure (NaFe^II₆Fe^III₃(OH)₁₈(SO₄)_2(s); GR_Na,SO4). The compound was synthesised by aerial oxidation of Fe(OH)_2(s) in the presence of NaOH. This paper reports on its free energy of formation .Freshly synthesised GR_Na,SO4 was titrated with 0.5 M H₂SO₄ in an inert atmosphere at 25 °C, producing dissolved Fe²⁺ and magnetite or goethite. Solution concentrations, PHREEQC and the MINTEQ database were used to calculate reaction constants for the reactions:

     

Solubility of pyromorphite Pb5(PO4)3Cl-mimetite Pb5(AsO4)3Cl solid solution series

Pyromorphite Pb₅(PO₄)₃Cl and mimetite Pb₅(AsO₄)₃Cl are isostructural minerals with apatite. Due to their high environmental stability, they have gained considerable attention as metals sequestration agents in water treatment and contaminated soil remediation. Pyromorphite and mimetite can form a continuous solid solution series in near-Earth surface environments. Precipitation of the end members and intermediate members of the series is likely to occur in the areas where the cost-effective in situ immobilization reclamation method, based on phosphate amendments, is applied. In contrast to the widely studied thermodynamic parameters of pyromorphite and mimetite, knowledge of the thermodynamics of their solid solutions is sparse. To supplement the data, a number of compounds from the pyromorphite-mimetite series were synthesized at room temperature using a method to simulate the conditions in the near-Earth surface environments. Afterwards, batch dissolution and dissolution-recrystallization experiments of seven synthesized precipitates were conducted at 25 °C, pH = 2 and in a 0.05 M KNO₃ background electrolyte. The experiments were carried out for a period of 6 (dissolution) and 14 (dissolution-recrystallization) months. A plateau in the [Pb] evolution patterns was used to determine equilibrium. All seven dissolutions were congruent, and the ionic activity products (IAP) of the minerals from the pyromorphite-mimetite solid solution series were calculated based on the dissolution reaction: . The IAPs for pyromorphite and mimetite exhibit a significant difference in values over three orders of magnitude between approximately 10⁻⁷⁹ for pyromorphite and approximately 10⁻⁷⁶ for mimetite. The series appeared to be ideal, and Lippmann and Roozboom diagrams were used for better understanding of its thermodynamics. The results indicated a strong tendency of pyromorphite to partition into the solid phase in the series, which explains some of the naturally observed phenomena. The improvement of the lattice stability of the mimetite due to isostructural phosphate substitutions in anionic sites was observed. The thermodynamic data reported in this study supplement existing databases used in geochemical modeling.     

Density functional theory study and kinetic analysis of the formation mechanism of Al30O8(OH)56(H2O)26 (Al30) in aqueous solution

The formation mechanism of Al₃₀O₈(OH)₅₆(H₂O)₂₆¹⁸⁺ (Al₃₀) has been investigated by the density functional theory based on the supermolecule model and kinetic analysis on the ²⁷Al nuclear magnetic resonance (NMR) experimental results in monitoring Al₃₀ synthesis process. The theoretical chemistry calculations on the four possible schemes show that δ-Na-Al₁₃ is the reasonable intermediate followed by the substitution of Na with Al to form δ-Al₁₄, and Na⁺ plays an important role in stabilizing the intermediate (δ-Na-Al₁₃) in the transformation. The kinetic analysis on the ²⁷Al NMR experimental data indicates that ε-Al₁₃ decomposes and isomerizes in the formation of Al₃₀, while Al monomers facilitate the decomposition of ε-Al₁₃ and so the isomerization of ε-isomers to δ-isomers effectively. The favorable formation mechanism of Al₃₀ includes three steps: (1) ε-Al₁₃ decomposes and rearranges into the isomer δ-Al₁₃; (2) Na⁺ reacts with δ-Al₁₃ to stabilize the intermediate δ-Na-Al₁₃, followed by Al monomers replacing Na to form δ-Al₁₄; (3) δ-Al₁₄ reacts with the Al monomers in the solution to finally form Al₃₀. Both Al monomers and Na⁺ are important in the transformation. Al monomers are the basic building units and helpful to the isomerization while Na⁺ can well stabilize the isomer δ-Al₁₃ to yield intermediate δ-Na-Al₁₃. The results also show that other isomers of ε-Al₁₃ (β-Al₁₃ and α-Al₁₃) form in the formation of Al₃₀, and their calculated ²⁷Al NMR tetrahedral resonance shifts are consistent with the experimental ²⁷Al NMR tetrahedral signals in the preparation process of Al₃₀.     

The flux of oxygen from the basal surface of gibbsite (α-Al(OH)3) at equilibrium

Experiments were conducted on gibbsite to determine whether oxygen-isotope exchange rates at hydroxyl bridges (μ₂-OH) on the basal sheet exhibit similar reactivity trends as in large aluminum polyoxocations, for which high-quality kinetic data exist. We followed the exchange of ¹⁸O from the mineral surface to solution by using a high-surface-area solid that had been enriched to tens of percent in ¹⁸O. To establish this high enrichment, we initially react the solid hydrothermally with highly enriched H₂¹⁸O in order to tag all oxygens near the mineral surface, and then back exchange the most reactive oxygens with isotopically normal water. This enrichment procedure isolates ¹⁸O into the least-reactive sites, which are presumably μ₂-OH on the basal surface. By analogy with aqueous aluminum complexes, including large multimers, the η-OH₂ sites exchange within fractions of a second and should be isotopically normal using this procedure.When suspended in isotopically normal electrolyte solutions, we find that the rates of release of ¹⁸O from the mineral fall close to the rates of dissolution. The lack of steady isotopic exchange of μ₂-OH on gibbsite surfaces contrasts with the aluminum polyoxocations, where the μ₂-OH exchange many hundreds of times with bulk water molecules before the molecule dissociates. Additional experiments were conducted in solutions at near-neutral pH to determine the flux of oxygens at conditions near thermodynamic equilibrium. As in more acidic solutions, rates are close to values expected from dissolution of the mineral and there is no evidence for steady exchange of hydroxyl bridges with water molecules in the bulk solution.     

Potentiometric and F nuclear magnetic resonance spectroscopic study of fluoride substitution in the GaAl12 polyoxocation: implications for aluminum (hydr)oxide mineral surfaces

Fluoride replacement of oxygens in the GaO₄Al₁₂(OH)₂₄(H₂O)127+(aq) molecule [GaAl₁₂] was studied via ¹⁹F nuclear magnetic resonance (NMR) at 4 < pH < 5 and 278 K in order to elucidate similar reactions at the surfaces of clays. Peaks are identified in the ¹⁹F-NMR spectra that correspond to both terminal and bridging fluorides on the GaAl₁₂ molecule, with relative peak positions similar to those previously identified in fluoridated aluminum (hydr)oxide mineral surfaces (Nordin, J. P., Sullivan, D. J., Phillips, B. L., and Casey, W. H. [1999], “Mechanisms for fluoride-promoted dissolution of bayerite [β-Al(OH)₃(s)] and boehmite [γ-AlOOH(s)]-¹⁹F-NMR spectroscopy and aqueous surface chemistry,” Geochim. Cosmochim. Acta63, 3513-3524). Fluoride substitutes for oxygen at three different sites in the GaAl₁₂ molecule, but at dramatically different rates.The kinetics of fluoride substitution follow a rate law that includes parallel and reversible transfer of fluoride from nonbridging sites to the two bridging sites. The essential features of the rate law are as follows: (1) fluoride replaces bound water molecules (η-OH₂) within minutes at 278 K at rates that are quantitatively similar to fluoride uptake by Al(H₂O)63+(aq) to form AlF²⁺(aq) at similar conditions; (2) fluoride substitutes onto the two topologically distinct μ₂-OH sites at different rates, as was previously observed for oxygen exchange, but here, the reaction is complete in hours to days at 278 K. Most importantly, rates of fluoride substitution onto μ₂-OH sites are 10² times more rapid than the corresponding rates of oxygen exchange with bulk waters, indicating that fluoride considerably labilizes the molecule, as is also observed at the surfaces of minerals. The largest cause of this labilization is the reduced molecular charge on the GaAl₁₂ upon replacement of bound waters by fluoride, which for mineral surfaces corresponds to a reduction in surface charge density.     

Solid-liquid equilibria of Mg(OH)2(cr) and Mg2(OH)3Cl·4H2O(cr) in the system Mg-Na-H-OH-Cl-H2O at 25°C

The solubility of crystalline Mg(OH)₂(cr) was determined by measuring the equilibrium H⁺ concentration in water, 0.01-2.7 m MgCl₂, 0.1-5.6 m NaCl, and in mixtures of 0.5 and 5.0 m NaCl containing 0.01-0.05 m MgCl₂. In MgCl₂ solutions above 2 molal, magnesium hydroxide converted into hydrated magnesium oxychloride. The solid-liquid equilibrium of Mg₂(OH)₃Cl·4H₂O(cr) was studied in 2.1-5.2 m MgCl₂. Using known ion interaction Pitzer coefficients for the system Mg-Na-H-OH-Cl-H₂O (25°C), the following equilibrium constants at I = 0 are calculated:

     

Stable boron isotope fractionation between dissolved B(OH)3 and B(OH)4

The stable boron isotope ratio (¹¹B/¹⁰B) in marine carbonates is used as a paleo-pH recorder and is one of the most promising paleo-carbonate chemistry proxies. Understanding the thermodynamic basis of the proxy is of fundamental importance, including knowledge on the equilibrium fractionation factor between dissolved boric acid, B(OH)₃, and borate ion, B(OH)₄⁻ (, hereafter α_(B3-B4)). However, this factor has hitherto not been determined experimentally and a theoretically calculated value (Kakihana and Kotaka, 1977, hereafter KK77) has therefore been widely used. I examine the calculations underlying this value. Using the same spectroscopic data and methods as KK77, I calculate the same α_(B3−B4) = 1.0193 at 300 K. Unfortunately, it turns out that in general the result is sensitive to the experimentally determined vibrational frequencies and the theoretical methods used to calculate the molecular forces. Using analytical techniques and ab initio molecular orbital theory, the outcome for α_(B3-B4) varies between ∼1.020 and ∼1.050 at 300 K. However, several arguments suggest that α_(B3-B4) ? 1.030. Measured isotopic shifts in various ¹⁰B-, ²D-, and ¹⁸O-labeled isotopomers do not provide a constraint on stable boron isotope fractionation. I conclude that in order to anchor the fundamentals of the boron pH proxy, experimental work is required. The critics of the boron pH proxy should note, however, that uncertainties in α_(B3-B4) do not bias pH reconstructions provided that organism-specific calibrations are used.     

Phosphoinnelite, Ba4Na3Ti3Si4O14(PO4,SO4)2(O,F)3, a new mineral species from peralkaline pegmatite of the Kovdor pluton, Kola Peninsula

Phosphoinnelite, an analogue of innelite with P > S, has been found in a peralkaline pegmatite vein crosscutting calcite carbonatite at the phlogopite deposit, Kovdor pluton, Kola Peninsula. Cancrinite (partly replaced with thomsonite-Ca), orthoclase, aegirine-augite, pectolite, magnesioarfvedsonite, golyshevite, and fluorapatite are associated minerals. Phosphoinnelite occurs as lath-shaped crystals up to 0.2 × 1 × 6 mm in size, which are combined typically in bunch-, sheaf-, and rosettelike segregations. The color is yellow-brown, with vitreous luster on crystal faces and greasy luster on broken surfaces. The mineral is transparent. The streak is pale yellowish. Phosphoinnelite is brittle, with perfect cleavage parallel to the {010} and good cleavage parallel to the {100}; the fracture is stepped. The Mohs hardness is 4.5 to 5. Density is 3.82 g/cm³ (meas.) and 3.92 g/cm³ (calc.). Phosphoinnelite is biaxial (+), α = 1.730, β = 1.745, and γ = 1.764, 2V (meas.) is close to 90°. Optical orientation is Z^c ∼ 5°. Chemical composition determined by electron microprobe is as follows (wt %): 6.06 Na₂O, 0.04 K₂O, 0.15 CaO, 0.99 SrO, 41.60 BaO, 0.64 MgO, 1.07 MnO, 1.55 Fe₂O₃, 0.27 Al₂O₃, 17.83 SiO₂, 16.88 TiO₂, 0.74 Nb₂O₅, 5.93 P₂O₅, 5.29 SO₃, 0.14 F, −O=F₂ = −0.06, total is 99.12. The empirical formula calculated on the basis of (Si,Al)₄O₁₄ is (Ba_3.59Sr_0.13K_0.01)_Σ3.73(Na_2.59Mg_0.21Ca_0.04)_Σ3.04(Ti_2.80Fe _0.26 ³⁺ Nb_0.07)_Σ3.13[(Si_3.93Al_0.07)_Σ4O₁₄(P_1.11S_0.87)_Σ1.98O_7.96](O_2.975F_0.10)_Σ3.075. The simplified formula is Ba₄Na₃Ti₃Si₄O₁₄(PO₄,SO₄)₂(O,F)₃. The mineral is triclinic, space group P or P1. The unit cell dimensions are a = 5.38, b = 7.10, c = 14.76 ?; α = 99.00°, β = 94.94°, γ = 90.14°; and V = 555 ?³, Z = 1. The strongest lines of the X-ray powder pattern [d, ? in (I)(hkl)] are: 14.5(100)(001), 3.455(40)(103), 3.382(35)(0 2), 2.921(35)(005), 2.810(40)(1 4), 2.683(90)(200, 01), 2.133(80)( 2), 2.059(40)(204, 1 3, 221), 1.772(30)(0 1, 1 7, 2 2, 2 3). The infrared spectrum is demonstrated. An admixture of P substituting S has been detected in the innelite samples from the Inagli pluton (South Yakutia, Russia). An innelite-phosphoinnelite series with a variable S/P ratio has been discovered. The type material of phosphoinnelite has been deposited at the Fersman Mineralogical Museum, Russian Academy of Sciences, Moscow. Original Russian Text ? I.V. Pekov, N.V. Chukanov, I.M. Kulikova, D.I. Belakovsky, 2006, published in Zapiski Rossiiskogo Mineralogicheskogo Obshchestva, 2006, No. 3, pp. 52–60. Considered and recommended by the Commission on New Minerals and Mineral Names, Russian Mineralogical Society, May 9, 2005. Approved by the Commission on New Minerals and Mineral Names, International Mineralogical Association, July 4, 2005 (proposal 2005-022).     

Oxidation of Sb(III) to Sb(V) by O2 and H2O2 in aqueous solutions

The rates of Sb(III) oxidation by O₂ and H₂O₂ were determined in homogeneous aqueous solutions. Above pH 10, the oxidation reaction of Sb(III) with O₂ was first order with respect to the Sb(III) concentration and inversely proportional to the H⁺ concentrations at a constant O₂ content of 0.22 × 10⁻³ M. Pseudo-first-order rate coefficients, k_obs, ranged from 3.5 × 10⁻⁸ s⁻¹ to 2.5 × 10⁻⁶ s⁻¹ at pH values between 10.9 and 12.9. The relationship between k_obs and pH was:

     

Low-temperature heat capacities of synthetic pyrope,grossular, and pyrope60grossular40

The heat capacities of synthetic pyrope (Mg₃Al₂Si₂O₁₂), grossular (Ca₃Al₂Si₃O₁₂) and a solid solution pyrope₆₀grossular₄₀ (Mg_1.8Ca_1.2Al₂Si₃O₁₂) have been measured by adiabatic calorimetry in the temperature range 10–350 K. The samples were crystallized from glasses in a conventional piston-cylinder apparatus.The molar thermophysical properties at 298.15 K (J mol^?1 K^?1) are:

     

17.

Thermodynamics of AFm-(I₂, SO₄) solid solution and of its end-members in aqueous media     

Laure Aimoz  Dmitrii A. Kulik  Erich Wieland  Enzo Curti  Barbara Lothenbach  Urs Mäder 《Applied Geochemistry》2012

     

18.

Solubility of Fe-ettringite (Ca₆[Fe(OH)₆]₂(SO₄)₃ · 26H₂O)     

Göril Möschner  Barbara Lothenbach  Andrea Ulrich  Ruben Kretzschmar 《Geochimica et cosmochimica acta》2008,72(1):1-18

The solubility of Fe-ettringite (Ca₆[Fe(OH)₆]₂(SO₄)₃ · 26H₂O) was measured in a series of precipitation and dissolution experiments at 20 °C and at pH-values between 11.0 and 14.0 using synthesised material. A time-series study showed that equilibrium was reached within 180 days of ageing. After equilibrating, the solid phases were analysed by XRD and TGA while the aqueous solutions were analysed by ICP-OES (calcium, sulphur) and ICP-MS (iron). Fe-ettringite was found to be stable up to pH 13.0. At higher pH-values Fe-monosulphate (Ca₄[Fe(OH)₆]₂(SO₄) · 6H₂O) and Fe-monocarbonate (Ca₄[Fe(OH)₆]₂(CO₃) · 6H₂O) are formed. The solubilities of these hydrates at 25 °C are:      

19.

Calcite dissolution kinetics in the system CaCO₃-H₂O-CO₂ at high undersaturation     

Georg Kaufmann  Wolfgang Dreybrodt 《Geochimica et cosmochimica acta》2007,71(6):1398-1410

Dissolution rates of limestone covered by a water film open to a CO₂-containing atmosphere are controlled by the chemical composition of the CaCO₃-H₂O-CO₂ solution at the water-mineral interface. This composition is determined by the Ca²⁺-concentration at this boundary, conversion of CO₂ into H⁺ and in the solution, and by diffusional mass transport of the dissolved species from and towards the water-limestone interface. A system of coupled diffusion-reaction equations for Ca²⁺, , and CO₂ is derived. The Ca²⁺ flux rates at the surface of the mineral are defined by the PWP-empirical rate law. These flux rates by the rules of stoichiometry must be equal to the flux rates of CO₂ across the air-water interface. In the solution, CO₂ is converted into H⁺ and . At low water-film thickness this reaction becomes rate limiting. The time dependent diffusion-reaction equations are solved for free drift dissolution by a finite-difference scheme, to obtain the dissolution rate of calcite as a function of the average calcium concentration in the water film. Dissolution rates are obtained for high undersaturation. The results reveal two regimes of linear dissolution kinetics, which can be described by a rate law F = α_i(m_ic_eq − c), where c is the calcium concentration in the water film, c_eq the equilibrium concentration with respect to calcite. For index i = 0, a fast rate law, which here is reported for the first time, is found with α₀ = 3 × 10⁻⁶ m s⁻¹ and m₀ = 0.3. For c > m₀c_eq, a slow rate law is valid with α₁ = 3 × 10⁻⁷ m  s⁻¹ and m₁ = 1, which confirms earlier work. The numbers given above are valid for film thickness of several tenths of a millimetre and at 20 °C. These rates are proven experimentally, using a flat inclined limestone plate covered by a laminar flowing water film injected at an input point with known flow rate Q and calcium concentration. From the concentration measured after flow distance x the dissolution rates are determined. These experiments have been performed at a carbon-dioxide pressure of 0.00035 atm and also of 0.01 atm. The results are in good agreement to the theoretical predictions.     

20.

Oxyphlogopite K(Mg,Ti,Fe)₃[(Si,Al)₄O₁₀](O,F)₂: A new mineral species of the mica group     

N. V. Chukanov  A. A. Mukhanova  R. K. Rastsvetaeva  D. I. Belakovsky  S. M?ckel  O. V. Karimova  S. N. Britvin  S. V. Krivovichev 《Geology of Ore Deposits》2011,53(7):583-590

Oxyphlogopite is a new mica-group mineral with the idealized formula K(Mg,Ti,Fe)₃[(Si,Al)₄O₁₀](O,F)₂. The holotype material came from a basalt quarry at Mount Rothenberg near Mendig at the Eifel volcanic complex in Rhineland-Palatinate, Germany. The mineral occurs as crystals up to 4 × 4 × 0.2 mm in size encrusting cavity walls in alkali basalt. The associated minerals are nepheline, plagioclase, sanidine, augite, diopside, and magnetite. Its color is dark brown, its streak is brown, and its luster is vitreous. D _meas = 3.06(1) g/cm³ (flotation in heavy liquids), and D _calc = 3.086 g/cm³. The IR spectrun does not contain bands of OH groups. Oxyphlogopite is biaxial (negative); α = 1.625(3), β = 1.668(1), and γ = 1.669(1); and 2V _meas = 16(2)° and 2V _calc = 17°. The dispersion is strong; r < ν. The pleochroism is medium; X > Y > Z (brown to dark brown). The chemical composition is as follows (electron microprobe, mean of 5 point analyses, wt %; the ranges are given in parentheses; the H₂O was determined using the Alimarin method; the Fe²⁺/Fe³⁺ was determined with X-ray emission spectroscopy): Na₂O 0.99 (0.89–1.12), K₂O 7.52 (7.44–7.58), MgO 14.65 (14.48–14.80), CaO 0.27 ((0.17–0.51), FeO 4.73, Fe₂O₃ 7.25 (the range of the total iron in the form of FeO is 11.09–11.38), Al₂O₃ 14.32 (14.06–14.64), Cr₂O₃ 0.60 (0.45–0.69), SiO₂ 34.41 (34.03–34.66), TiO₂ 12.93 (12.69–13.13), F 3.06 (2.59–3.44), H₂O 0.14; O=F₂ −1.29; 99/58 in total. The empirical formula is (K_0.72Na_0.14Ca_0.02)(Mg_1.64Ti_0.73Fe_0.30²⁺ Fe_0.27³⁺Cr_0.04)_Σ2.98(Si_2.59Al_1.27Fe_0.14³⁺ O₁₀) O_1.20F_0.73(OH)_0.07. The crystal structure was refined on a single crystal. Oxyphlogopite is monoclinic with space group C2/m; the unit-cell parameters are as follows: a = 5.3165(1), b = 9.2000(2), c = 10.0602(2) ?, β = 100.354(2)°. The presence of Ti results in the strong distortion of octahedron M(2). The strongest lines of the X-ray powder diffraction pattern [d, ? (I, %) [hkl]] are as follows: 9.91(32) [001], 4.53(11) 110], 3.300(100) [003], 3.090(12) [112], 1.895(21) [005], 1.659(12) [−135], 1.527(16) [−206, 060]. The type specimens of oxyphlogopite are deposited at the Fersman Mineralogical Museum in Moscow, Russia; the registration numbers are 3884/2 (holotype) and 3884/1 (cotype).     

	Cop	So298?So0	Ho298?Ho0/T
Pyrope	325.31	266.27	47852
Grossular	333.17	260.12	47660
Py60Gr40	328.32	268.32	47990

Solubility of Fe-ettringite (Ca6[Fe(OH)6]2(SO4)3 · 26H2O)

The solubility of Fe-ettringite (Ca₆[Fe(OH)₆]₂(SO₄)₃ · 26H₂O) was measured in a series of precipitation and dissolution experiments at 20 °C and at pH-values between 11.0 and 14.0 using synthesised material. A time-series study showed that equilibrium was reached within 180 days of ageing. After equilibrating, the solid phases were analysed by XRD and TGA while the aqueous solutions were analysed by ICP-OES (calcium, sulphur) and ICP-MS (iron). Fe-ettringite was found to be stable up to pH 13.0. At higher pH-values Fe-monosulphate (Ca₄[Fe(OH)₆]₂(SO₄) · 6H₂O) and Fe-monocarbonate (Ca₄[Fe(OH)₆]₂(CO₃) · 6H₂O) are formed. The solubilities of these hydrates at 25 °C are:      

Calcite dissolution kinetics in the system CaCO3-H2O-CO2 at high undersaturation

Dissolution rates of limestone covered by a water film open to a CO₂-containing atmosphere are controlled by the chemical composition of the CaCO₃-H₂O-CO₂ solution at the water-mineral interface. This composition is determined by the Ca²⁺-concentration at this boundary, conversion of CO₂ into H⁺ and in the solution, and by diffusional mass transport of the dissolved species from and towards the water-limestone interface. A system of coupled diffusion-reaction equations for Ca²⁺, , and CO₂ is derived. The Ca²⁺ flux rates at the surface of the mineral are defined by the PWP-empirical rate law. These flux rates by the rules of stoichiometry must be equal to the flux rates of CO₂ across the air-water interface. In the solution, CO₂ is converted into H⁺ and . At low water-film thickness this reaction becomes rate limiting. The time dependent diffusion-reaction equations are solved for free drift dissolution by a finite-difference scheme, to obtain the dissolution rate of calcite as a function of the average calcium concentration in the water film. Dissolution rates are obtained for high undersaturation. The results reveal two regimes of linear dissolution kinetics, which can be described by a rate law F = α_i(m_ic_eq − c), where c is the calcium concentration in the water film, c_eq the equilibrium concentration with respect to calcite. For index i = 0, a fast rate law, which here is reported for the first time, is found with α₀ = 3 × 10⁻⁶ m s⁻¹ and m₀ = 0.3. For c > m₀c_eq, a slow rate law is valid with α₁ = 3 × 10⁻⁷ m  s⁻¹ and m₁ = 1, which confirms earlier work. The numbers given above are valid for film thickness of several tenths of a millimetre and at 20 °C. These rates are proven experimentally, using a flat inclined limestone plate covered by a laminar flowing water film injected at an input point with known flow rate Q and calcium concentration. From the concentration measured after flow distance x the dissolution rates are determined. These experiments have been performed at a carbon-dioxide pressure of 0.00035 atm and also of 0.01 atm. The results are in good agreement to the theoretical predictions.     

Oxyphlogopite K(Mg,Ti,Fe)3[(Si,Al)4O10](O,F)2: A new mineral species of the mica group

Oxyphlogopite is a new mica-group mineral with the idealized formula K(Mg,Ti,Fe)₃[(Si,Al)₄O₁₀](O,F)₂. The holotype material came from a basalt quarry at Mount Rothenberg near Mendig at the Eifel volcanic complex in Rhineland-Palatinate, Germany. The mineral occurs as crystals up to 4 × 4 × 0.2 mm in size encrusting cavity walls in alkali basalt. The associated minerals are nepheline, plagioclase, sanidine, augite, diopside, and magnetite. Its color is dark brown, its streak is brown, and its luster is vitreous. D _meas = 3.06(1) g/cm³ (flotation in heavy liquids), and D _calc = 3.086 g/cm³. The IR spectrun does not contain bands of OH groups. Oxyphlogopite is biaxial (negative); α = 1.625(3), β = 1.668(1), and γ = 1.669(1); and 2V _meas = 16(2)° and 2V _calc = 17°. The dispersion is strong; r < ν. The pleochroism is medium; X > Y > Z (brown to dark brown). The chemical composition is as follows (electron microprobe, mean of 5 point analyses, wt %; the ranges are given in parentheses; the H₂O was determined using the Alimarin method; the Fe²⁺/Fe³⁺ was determined with X-ray emission spectroscopy): Na₂O 0.99 (0.89–1.12), K₂O 7.52 (7.44–7.58), MgO 14.65 (14.48–14.80), CaO 0.27 ((0.17–0.51), FeO 4.73, Fe₂O₃ 7.25 (the range of the total iron in the form of FeO is 11.09–11.38), Al₂O₃ 14.32 (14.06–14.64), Cr₂O₃ 0.60 (0.45–0.69), SiO₂ 34.41 (34.03–34.66), TiO₂ 12.93 (12.69–13.13), F 3.06 (2.59–3.44), H₂O 0.14; O=F₂ −1.29; 99/58 in total. The empirical formula is (K_0.72Na_0.14Ca_0.02)(Mg_1.64Ti_0.73Fe_0.30²⁺ Fe_0.27³⁺Cr_0.04)_Σ2.98(Si_2.59Al_1.27Fe_0.14³⁺ O₁₀) O_1.20F_0.73(OH)_0.07. The crystal structure was refined on a single crystal. Oxyphlogopite is monoclinic with space group C2/m; the unit-cell parameters are as follows: a = 5.3165(1), b = 9.2000(2), c = 10.0602(2) ?, β = 100.354(2)°. The presence of Ti results in the strong distortion of octahedron M(2). The strongest lines of the X-ray powder diffraction pattern [d, ? (I, %) [hkl]] are as follows: 9.91(32) [001], 4.53(11) 110], 3.300(100) [003], 3.090(12) [112], 1.895(21) [005], 1.659(12) [−135], 1.527(16) [−206, 060]. The type specimens of oxyphlogopite are deposited at the Fersman Mineralogical Museum in Moscow, Russia; the registration numbers are 3884/2 (holotype) and 3884/1 (cotype).