Composition,Structure, and Conditions of Formation of Fluorine-Bearing Sodalite: Experimental Evidence

Fluoro-sodalite was synthesized for the first time at temperatures of 400–800°C and H₂O pressures of 1–2 kbar in the Si–Al–Na–H–O–F system. X-ray diffraction and infrared spectroscopic investigations showed that fluorine is incorporated in the sodalite structure as anionic octahedral groups, [AlF₆]^3–, the number of which can vary from 0 to 1. Correspondingly, the end-members of the F-sodalite series are Na₇(H₂O)₈[Si₅Al₇O₂₄] and Na₈(AlF₆)(H₂O)₄[Si₇Al₅O₂₄]. Depending on the composition of the system, F-sodalite associates at 500–650°C with nepheline, albite, cryolite, and villiaumite, which are joined by analcime below 500°C and aluminosilicate melt above 650°C. Fluorine-bearing sulfate–chlorine-sodalite was found for the first time in a pegmatite sample from the Lovozero massif. The highest fraction of the fluorine end-member in natural sodalite is 0.2. The incorporation of F into the sodalite structure requires much more energy compared with Cl^– and SO ₄ ^2- , because it is accompanied by a structural rearrangement and a transition from tetrahedral Al to octahedral Al.     

Thermodynamic study of calcic amphiboles

The paper reports original thermochemical data on six natural amphibole samples of different composition. The data were obtained by high-temperature melt solution calorimetry in a Tian–Calvet microcalorometer and include the enthalpies of formation from elements for actinolite Ca_1.95(Mg_4.4Fe _0.5 ²⁺ Al₀₁)[Si_8.0O₂₂](OH)₂(–12024 ± 13 kJ/mol) and Ca_2.0(Mg_2.9Fe _1.9 ²⁺ Fe _0.2 ³⁺ )[Si_7.8Al_0.2O₂₂](OH)₂, (–11462 ± 18 kJ/mol), and Na_0.1Ca_2.0(Mg_3.2Fe _1.6 ²⁺ Fe _0.2 ³⁺ )[Si_7.7Al_0.3O₂₂](OH)₂ (–11588 ± 14 kJ/mol); for pargasite Na_0.5K_0.5Ca_2.0-(Mg_3.4Fe _1.8 ²⁺ Al_0.8)[Si_6.2Al_1.8O₂₂](OH)₂ (–12316 ± 10 kJ/mol) and Na_0.8K_0.2Ca_2.0(Mg_2.8Fe _1.3 ³⁺ Al_0.9) [Si_6.1Al_1.9O₂₂](OH)₂ (–12 223 ± 9 kJ/mol); and for hastingsite Na_0.3K_0.2Ca_2.0(Mg_0.4Fe _1.3 ²⁺ Fe _0.9 ³⁺ Al_0.2) [Si_6.4Al_1.6O₂₂](OH)₂ (?10909 ± 11 kJ/mol). The standard entropy, enthalpy, and Gibbs free energy of formation are estimated for amphiboles of theoretical composition: end members and intermediate members of the isomorphic series tremolite–ferroactinolite, edenite–ferroedenite, pargasite–ferropargasite, and hastingsite.     

Boron in magnesium minerals of the humite group

Based on microprobe analysis and IR-spectroscopy of a representative collection of magnesium minerals of the humite group (282 samples from 80 various geological-genetic occurrences all over the world), it was shown for the first time that these minerals typically concentrate trace boron (from 0.5 to 4.9 wt % B₂O₃ in 63 samples). The diagnostic bands of B-O stretching vibrations in IF-spectra of magnesium minerals of the humite group occur within the 1170–1190, 1262–1289, and 1306–1331 cm^?1 ranges and are regularly shifted to the low frequencies in a norbergite-chondrodite-humite-clinohumite series. Boron isomorphically replaces silicon in tetrahedra, probably, by Pertsev’s scheme: Si⁴⁺ + O^2? → B³⁺ + (F,OH)^?.     

Li-Tosudite: X-Ray Diffraction,IR Spectroscopic,Thermal, and Thermochemical Studies

The paper reports data obtained in the course of a comprehensive physicochemical study of Li-tosudite, a mixed-layer mineral from hydrothermally altered rocks in western Chukotka, Russia, whose formula was reliably established. The enthalpy of formation of Li-tosudite from Chukotka, Ca_0.15(Li_0.9Mg_0.2Al_6.0)[Si_6.4Al_1.6O₂₀](OH)10 · 3.3H₂O, from elements was experimentally determined by melt solution calorimetry in a high-temperature Calvet microcalorimeter: Δ_fH _el ^o (298.15 К) =–15087 ± 26 kJ/mol. The standard entropy and Gibbs free energy of formation of this mineral were evaluated.     

Thermodynamic properties of Fe-rich smectite-nontronite

The results of thermochemical studies are reported for nontronite samples from the Pinares-de-Majari (Eastern Cuba) (Sample I) and Kempirsai serpentine massif (South Urals, Kazakhstan) (Sample II). The enthalpies of formation of dehydrated hydroxyl-bearing nontronites from elements were determined by melt dissolution calorimetry using high-temperature heat-flux Tiana-Calvet microcalorimeter: Δ _f H _el ^o (298.15 K): ?4958 ± 13 kJ/mol for Mg_0.4(Fe _1.5 ³⁺ Mg_0.4Ni_0.1)[Si_3.7Al_0.3O₁₀](OH)₂ (I) and ?5003.6 ± 8.0 kJ/mol for Mg_0.3Na_0.1Ca_0.1(Fe _1.4 ³⁺ Mg_0.5Ni_0.1)[Si_3.7Al_0.3O₁₀](OH)₂ (II). It was determined experimentally that the enthalpy of dehydration (removal of molecular adsorption and interlayer water) of the studied nontronites is 6 ± 2 kJ per 1 mole H₂O. The enthalpy of formation of nontronite of theoretical composition Mg_0.15Fe ₂ ³⁺ [Si_3.7Al_0.3]O₁₀(OH)₂ was estimated at ?4750 kJ/mol. The Gibbs free energies of formation of the nontronites were calculated.