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1.
The thermochemical study of two natural trioctahedral Mg–Fe chlorites—clinochlores was carried out using high-temperature melt solution calorimetry with a Tian–Calvet microcalorimeter. The enthalpies of formation of clinochlores of compositions (Mg4.9Fe 0.3 2+ Al0.8)[Si3.2Al0.8O10](OH)8 (–8811 ± 12 kJ/mol) and (Mg4.3Fe 0.7 2+ Al1.0)[Si3.0Al1.0O10](OH)8 (–8696 ± 13 kJ/mol) from elements were determined. The values of the standard entropies and the Gibbs energies of formation of the studied natural minerals as well as thermodynamic properties of Mg–Fe chlorites of theoretical composition were estimated.  相似文献   

2.
The paper reports results of an experimental thermochemical study (in a heat-flux Tian-Calvet microcalorimeter) of montmorillonite from (I) the Taganskoe and (II) Askanskoe deposits and (III) from the caldera of Uzon volcano, Kamchatka. The enthalpy of formation Δ f H el 0 (298.15 K) of dehydrated hydroxyl-bearing montmorillonite was determined by melt solution calorimetry: ?5677.6 ± 7.6 kJ/mol for Na0.3Ca0.1(Mg0.4Al1.6)[Si3.9Al0.1O10](OH)2 (I), ?5614.3 ± 7.0 kJ/mol for Na0.4K0.1(Ca0.1Mg0.3Al1.5Fe 0.1 3+ )[Si3.9Al0.1O10](OH)2 (II), ?5719 ± 11 kJ/mol for K0.1Ca0.2Mg0.2(Mg0.6Al1.3Fe 0.1 3+ ) [Si3.7Al0.3O10](OH)2 (III), and ?6454 ± 11 kJ/mol for water-bearing montmorillonite (I) Na0.3Ca0.1(Mg0.4Al1.6)[Si3.9Al0.1O10](OH)2 · 2.6H2O. The paper reports estimated enthalpy of formation for the smectite end members of the theoretical composition of K-, Na-, Mg-, and Ca-montmorillonite and experimental data on the enthalpy of dehydration (14 ± 2 kJ per mole of H2O) and dehydroxylation (166 ± 10 kJ per mole of H2O) for Na-montmorillonite.  相似文献   

3.
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 Mg0.4(Fe 1.5 3+ Mg0.4Ni0.1)[Si3.7Al0.3O10](OH)2 (I) and ?5003.6 ± 8.0 kJ/mol for Mg0.3Na0.1Ca0.1(Fe 1.4 3+ Mg0.5Ni0.1)[Si3.7Al0.3O10](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 Mg0.15Fe 2 3+ [Si3.7Al0.3]O10(OH)2 was estimated at ?4750 kJ/mol. The Gibbs free energies of formation of the nontronites were calculated.  相似文献   

4.
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, Ca0.15(Li0.9Mg0.2Al6.0)[Si6.4Al1.6O20](OH)10 · 3.3H2O, from elements was experimentally determined by melt solution calorimetry in a high-temperature Calvet microcalorimeter: ΔfH el o (298.15 К) =–15087 ± 26 kJ/mol. The standard entropy and Gibbs free energy of formation of this mineral were evaluated.  相似文献   

5.
The paper presents data on the thermochemical study (high-temperature melt calorimetry in a Tian–Calvet microcalorometer) of two natural Mg–Fe amphiboles: anthophyllite Mg2.0(Mg4.8Fe0.2 2+)[Si8.0O22](OH)2 from Kukh-i-Lal, southwestern Pamirs, Tajikistan, and gedrite Na0.4Mg2.0(Mg1.7Fe0.2 2+Al1.3)[Si6.3Al1.7O22](OH)2 from the Kola Peninsula, Russia. The enthalpy of formation from elements is obtained as–12021 ± 20 kJ/mol for anthophyllite and as–11545 ± 12 kJ/mol for gedrite. The standard entropy, enthalpy, and Gibbs energy of formation are evaluated for Mg–Fe amphiboles of theoretical composition.  相似文献   

6.
The crystal structures of synthetic K-dravite [XKYMg 3 Z Al 6 T Si6O18(BO3) 3 V (OH) 3 W (OH)], dravite [XNaYMg 3 Z Al 6 T Si6O18(BO3) 3 V (OH) 3 W (OH)], oxy-uvite [XCaYMg 3 Z Al 6 T Si6O18(BO3) 3 V (OH) 3 W O], and magnesio-foitite [X?Y(Mg2Al)ZAl 6 T Si6O18(BO3) 3 V (OH) 3 W (OH)] are investigated by polarized Raman spectroscopy, single-crystal structure refinement (SREF), and powder X-ray diffraction. The use of compositionally simple tourmalines characterized by electron microprobe analysis facilitates the determination of site occupancy in the SREF and band assignment in the Raman spectra. The synthesized K-dravite, oxy-uvite, and magnesio-foitite have significant Mg–Al disorder between their octahedral sites indicated by their respective average 〈Y–O〉 and 〈Z–O〉 bond lengths. The Y- and Z-site compositions of oxy-uvite (YMg1.52Al1.48(10) and ZAl4.90Mg1.10(15)) and magnesio-foitite (YAl1.62Mg1.38(18) and ZAl4.92Mg1.08(24)) are refined from the electron densities at each site. The Mg–Al ratio of the Y and Z sites is also determined from the relative integrated peak intensities of the Raman bands in the O–H stretching vibrational range (3250–3850 cm?1), producing values in good agreement with the SREF data. The unit cell volume of tourmaline increases from magnesio-foitite (1558.4(3) Å3) to dravite (1569.5(4)–1571.7(3) Å3) to oxy-uvite (1572.4(2) Å3) to K-dravite (1588.1(2) Å3), mainly due to lengthening of the crystallographic c-axis. The increase in the size of the X-site coordination polyhedron from dravite (Na) to K-dravite (K) is accommodated locally in the crystal structure, resulting in the shortening of the neighboring O1–H1 bond. In oxy-uvite, Ca2+ is locally associated with a deprotonated W (O1) site, whereas vacant X sites are neighbored by protonated W (O1) sites. Increasing the size of the X-site-occupying ion does not detectably affect bonding between the other sites; however, the higher charge of Ca and the deprotonated W (O1) site in oxy-uvite are correlated to changes in the lattice vibration Raman spectrum (100–1200 cm?1), particularly for bands assigned to the T 6O18 ring. The Raman spectrum of magnesio-foitite shows significant deviations from those of K-dravite, dravite, and oxy-uvite in both the lattice and O–H stretching vibrational ranges (100–1200 and 3250–3850 cm?1, respectively). The vacant X site is correlated with long- and short-range changes in the crystal structure, i.e., deformation of the T 6O18 ring and lengthening of the O1–H1 and O3–H3 bonds. However, X-site vacancies in K-dravite, dravite, and oxy-uvite result only in the lengthening of the neighboring O1–H1 bond and do not result in identifiable changes in the lattice-bonding environment.  相似文献   

7.
Kinetic studies of isothermal heating experiments (600–800° C) on aluminous pyroxenes (Mg0.942Fe 0.880 2+ Fe 0.068 3+ Mn0.016Ca0.010Al0.084) (Si1.848Al0.152) permit the determination of rate constant of isothermal disordering as 2.5457 E13(±1.4 E13) min?1. The activation energy is determined as 278 (±23) kJ/mol. Data on two other aluminous pyroxenes at 700° C indicate that the rate constant decreases significantly with increasing amount of trivalent cations. There is a similar but reverse correlation between the concentration of trivalent cations and the Fe2+-Mg equilibrium distribution between sites. The site distribution coefficient increases with increasing concentration of trivalent cations at constant temperature.  相似文献   

8.
The incorporation of hydrogen into ferrosilite, Fe-bearing enstatite and orthopyroxene containing different trivalent cations (Cr3+ and Al3+, Cr3+ and Fe3+) was investigated experimentally at 25 kbar. Hydrogen concentration was determined by FTIR-spectroscopy on oriented crystal sections and by secondary ion mass spectroscopy, whereas Mößbauer spectroscopy and optical spectroscopy were used to characterise the valence state of Fe in orthopyroxene. Results suggest that hydrogen incorporation in ferrosilite is achieved by a similar mechanism as in pure enstatite. In Cr-bearing samples, however, hydrogen incorporation is reduced by the presence of other trivalent cations by an increased tendency to form Tschermaks substitutions, e.g. Si T 4+ + Mg M1 2+ ? Al T 3+ + Cr M1 3+ . Thus, hydrogen solubility in natural orthopyroxenes from the Earth’s mantle, containing significant amounts of Cr3+, Al3+, and Fe3+, may be much more limited than expected from their trivalent cation content, as a large fraction of the trivalent cations does not participate in H-incorporating reactions as 2 Mg M1 2+ ? M M1 3+ + VM1 + H i + .  相似文献   

9.
The paper presents the results of a thermochemical and thermal study of cancrinite, (Na6.93Ca0.545K0.01)Σ7.485[(Si6.47Al5.48Fe0.05)Σ12O24](CO3)1.25 · 2.30 H2O, and cancrisilite, (Na7.17 Ca0.01)Σ7.18[(Si7.26Al4.70Fe0.04)Σ12O24][(CO3)1.05(OH)0.21(PO4)0.04(SO4)0.01] · 2.635 H2O, from the Khibina-Lovozero Complex, Kola Peninsula, Russia. Stages of the thermal decomposition of these minerals were studied using IR spectroscopy. The enthalpies of formation of the minerals from elements were determined by melt drop solution calorimetry: Δ f H el 0 (298.15 K) = ?14 490 ± 16 kJ/mol for cancrinite and ?14302 ± 17 kJ/mol for cancrisilite. The values of Δ f H el 0 (298.15 K), S o(298.15 K), and Δ f H el 0 (298.15 K) are determined for cancrinite and cancrisilite of theoretical composition.  相似文献   

10.
A new coexisting amphibole pair was recently found in the Jianshan iron deposit, Loufan of Shanxi Province, China. Electron microprobe analysis shows that the coexisting pair is composed of grünerite K0.001 (Na0.027 Ca0.073 Mn0.031 Fe 1.801 2+ )1.932 (Fe 2.948 2+ Mg1.964 Ti0.002 Al0.087)5Si8.069 O22.10(OH)2 and ferropargasite (K0.135 Na0.461)0.596 (Na0.088 Ca1.853 Mn0.005 Fe 0.072 2+ )2(Mn0.005Fe 2.789 2+ Mg0.875Ti0.021Fe 0.499 3+ Al0.812)5(Si6.103Al1.897)8O22.00(OH)2. The two kinds of amphiboles occur in amphibole schist not only as separate phenocrysts, but also are combined to form “single-crystal” phenocrysts in the form of topotactic intergrowths with the common c- and b-axes. The boundary between topotactic grünerite and ferropargasite is optically and chemically sharp. In comparison with the coexisting ferromagnesian amphibole and calcic amphibole pair discovered by predecessors, the newly discovered pair has lower Mg/Fe ratios and wider miscibility gaps.  相似文献   

11.
This contribution is finalized at the discussion of the magnetic structure of two samples, belonging to phlogopite–annite [sample TK, chemical composition IV(Si2.76Al1.24) VI(Al0.64Mg0.72 $ {\text{Fe}}_{1.45}^{2 + } $ Mn0.03Ti0.15) (K0.96Na0.05) O10.67 (OH)1.31 Cl0.02] and polylithionite–siderophyllite joints [sample PPB, chemical composition IV(Si3.14Al0.86)VI(Al0.75Mg0.01 $ {\text{Fe}}_{1.03}^{2 + } $ $ {\text{Fe}}_{1.03}^{3 + } $ Mn0.01Ti0.01Li1.09) (K0.99Na0.01) O10.00 (OH)0.65F1.35]. Samples differ for Fe ordering in octahedral sites, Fe2+/(Fe2+?+?Fe3+) ratio, octahedral composition, defining a different environment around Fe cations, and layer symmetry. Spin-glass behavior was detected for both samples, as evidenced by the dependency of the temperature giving the peak in the susceptibility curve from the frequency of the applied alternating current magnetic field. The crystal chemical features are associated to the different temperature at which the maximum in magnetic susceptibility is observed: 6?K in TK, where Fe is disordered in all octahedral sites, and 8?K in PPB sample, showing a smaller and more regular coordination polyhedron for Fe, which is ordered in the trans-site and in one of the two cis-sites.  相似文献   

12.

Polarized absorption spectra of natural piemontite (Ca1.802Mn 2+0.178 Mg0.025) (Mn 3+0.829 Fe 3+0.346 Al1.825) [(Si2.992Al0.008) O12OH], viridine (Al1.945Mn 3+0.033 Fe 3+0.063 Mg0.003) [O|Si0.970 O4], and kanonaite (Al1.291Mn 3+0.682 Fe 3+0.019 ) [O|Si1.006 O4] were measured at 295 and ca. 100 K. For piemontite, lowering the temperature resulted in a sharpening of broad bands in the 10 000–25 000 cm−1 region supporting their assignment to single ion Mn3+ in M3 non-centrosymmetric sites.

Alternatively, in kanonaite, temperature behaviour pointed to a slightly stronger influence of vibronic coupling on strong bands near 16 000 and 22 000 cm−1, which supported an interpretation of Mn3+ in nearly centrosymmetric M1 sites. Measurements at ca. 100 K show pronounced fine structure in the viridine spectra which is attributed to Fe3+. The ɛ values for Mn3+ spin-allowed bands in the three minerals lie in the range 18 to 227 [1·g-atom−1·cm−1].

For the same band and polarisation, ɛ values in Mn3+-bearing andalusite-type minerals viridine and kanonaite are the same, which indicates an absence of strong magnetic coupling effects between Mn3+ ions in the andalusite type structure down to ca. 100 K.

In silicates, the high ɛ values for Mn3+ spin-allowed bands, in comparison to those obtained for Fe2+ spin-allowed bands from sites of “similar distortion”, is attributed to a higher degree of covalency in the Mn3+-O bonds compared to the Fe2+-O bonds, as a result of the higher valence state of manganese.

  相似文献   

13.
Far from equilibrium, quasi-steady state dissolution rates of an iron rich chlorite (Mg2.76Fe2+1.90Fe3+0.07Al0.97)[Si2.48Al1.52O10](OH)8, have been measured as a function of H+ concentration for the pH range 3 to 10.5 and at 25°C. The rates were determined using a single pass flow through cell and with a time frame for observing the steady state condition of between 10 to 50 days. Rates are independent of the buffers used to control the pH, sample preparation, experimental methodology and chlorite composition. The results were collated with literature values allowing the rate to be expressed as a function of H+ as;
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14.
The mixed valence iron silicate deerite, Fe 6 2+ Fe 3 3+ O3[Si6O17](OH)5 whose crystal structure has only recently been fully determined, had been previously examined by both susceptibility measurements and Mössbauer spectroscopy. We reinterpret the Mössbauer measurements from Frank and Bunbury and show that all contradictions between the phenomena, observed in their experiments, and the mineralogical structure disappear when one accepts a thermally activated electron delocalisation associated with Fe2+ ? Fe3+ charge transfer.  相似文献   

15.
The solubility of Gd2Ti2O7 ceramic in acidic solutions (HCl and HClO4) was studied at 250°C and saturation vapor pressure within pH 2.5–5.2. The dissolution process occurs mainly via two reactions: 0.5 Gd2Ti2O7(cr) + 3H+ = Gd3+ + TiO2(cr) + 1.5 H2O at pH < 3 and 0.5Gd2Ti2O7(cr) + H+ + 0.5H2O = Gd(OH) 2 + TiO2(cr) at pH 3–5. The thermodynamic equilibrium constants were calculated at the 0.95 confidence level as log K (1) o = 4.12 ± 0.47; = ?0.97 ± 0.16 at 250°C. It was shown that Gd3+ undergoes hydrolysis in solutions with pH > 3, and the species Gd(OH) 2 + dominates up to at least pH 5. At pH < 3, Gd occurs in solutions as Gd3+. The second constant of Gd3+ hydrolysis was determined at 250°C as K o = ?5.09 ± 0.5, and the thermodynamic characteristics of the initial Gd2Ti2O7 solid phase were determined: S 298.15 o = 251.4 J/(mol K) and ΔfG 298.15 o = ?3630 ± 10 kJ/mol.  相似文献   

16.
Surface snow and lake water samples were collected at different locations around Indian station at Antarctica, Maitri, during December 2004–March 2005 and December 2006–March 2007. Samples were analyzed for major chemical ions. It is found that average pH value of snow is 6.1. Average pH value of lake water with low chemical content is 6.2 and of lake water with high chemical content is 6.5. The Na+ and Cl? are the most abundantly occurring ions at Antarctica. Considerable amount of SO 4 2? is also found in the surface snow and the lake water which is attributed to the oxidation of DMS produced by marine phytoplankton. Neutralization of acidic components of snow is mainly done by NH 4 + and Mg2+. The Mg2+, Ca2+ and K+ are nearly equally effective in neutralizing the acidic components in lake water. The NH 4 + and SO 4 2? occur over the Antarctica region mostly in the form of (NH4)2SO4.  相似文献   

17.
Manganocummingtonite occurs with spessartine, quartz and pyrolusite in the Chikmara area, Sausar fold belt, central India. Its composition is [Ca0.3–0.35(Mg3.3–3.5Mn1.6–1.8Fe2+ 1.4–1.5)(Si7.931–7.997Aliv 0.003–0.069)O22(OH1.5–2.0F0.0–0.5)] being fairly rich in Ca, which is indicative of metamorphic temperature in the amphibolite facies. The garnet contains 77.5% spessartine, 13% almandine and minor andradite, grossular and pyrope components. Unusually, there is no carbonate, pyroxene, pyroxmangite, rhodonite, magnetite or hematite. The available Al in the rock stabilized garnet and this mineral incorporated minor Fe3+ present in the rock as andradite component. The manganocummingtonite-garnet pairs developed at ～600°C during amphibolite facies metamorphism in low $X_{CO_2 } $ system, stabilized with $X_{Mn/(Mn + Fe^{2 + } + Mg)} $ = 0.25 to 0.28 in the amphibole and 0.85 in the garnet and formed under unusually low fO 2 conditions for the Sausar region, near channelized fluids which deposited quartz may have controlled the fO 2 .  相似文献   

18.
Batisivite has been found as an accessory mineral in the Cr-V-bearing quartz-diopside metamorphic rocks of the Slyudyanka Complex in the southern Baikal region, Russia. A new mineral was named after the major cations in its ideal formula (Ba, Ti, Si, V). Associated minerals are quartz, Cr-V-bearing diopside and tremolite; calcite; schreyerite; berdesinskiite; ankangite; V-bearing titanite; minerals of the chromite-coulsonite, eskolaite-karelianite, dravite-vanadiumdravite, and chernykhite-roscoelite series; uraninite; Cr-bearing goldmanite; albite; barite; zircon; and unnamed U-Ti-V-Cr phases. Batisivite occurs as anhedral grains up to 0.15–0.20 mm in size, without visible cleavage and parting. The new mineral is brittle, with conchoidal fracture. Observed by the naked eye, the mineral is black and opaque, with a black streak and resinous luster. Batisivite is white in reflected light. The microhardness (VHN) is 1220–1470 kg/mm2 (load is 30 g), the mean value is 1330 kg/mm2. The Mohs hardness is near 7. The calculated density is 4.62 g/cm3. The new mineral is weakly anisotropic and bireflected. The measured values of reflectance are as follows (λ, nm—R max ′ /R min ′ ): 440—17.5/17.0; 460—17.3/16.7; 480—17.1/16.5; 500—17.2/16.6; 520—17.3/16.7; 540—17.4/16.8; 560—17.5/16.8; 580—17.6/16.9; 600—17.7/17.1; 620—17.7/17.1; 640—17.8/17.1; 660—17.9/17.2; 680—18.0/17.3; 700—18.1/17.4. Batisivite is triclinic, space group P \(\overline 1\); the unit-cell dimensions are: a = 7.521(1) Å, b = 7.643(1) Å, c = 9.572(1) Å, α = 110.20°(1), β = 103.34°(1), γ = 98.28°(1), V = 487.14(7) Å3, Z = 1. The strongest reflections in the X-ray powder diffraction pattern [d, Å (I, %)(hkl)] are: 3.09(8)(12\(\overline 2\)); 2.84, 2.85(10)(021, 120); 2.64(8)(21\(\overline 3\)); 2.12(8)(31\(\overline 3\)); 1.785(8)(32\(\overline 4\)), 1.581(10)(24\(\overline 2\)); 1.432, 1.433(10)(322, 124). The chemical composition (electron microprobe, average of 237 point analyses, wt %) is: 0.26 Nb2O5, 6.16 SiO2, 31.76 TiO2, 1.81 Al2O3, 8.20 VO2, 26.27 V2O3, 12.29 Cr2O3, 1.48 Fe2O3, 0.08 MgO, 11.42 BaO; the total is 99.73. The VO2/V2O3 ratio has been calculated. The simplified empirical formula is (V 4.8 3+ Cr2.2V 0.7 4+ Fe0.3)8.0(Ti5.4V 0.6 4+ )6.0[Ba(Si1.4Al0.5O0.9)]O28. An alternative to the title formula could be a variety (with the diorthogroup Si2O7) V8Ti6[Ba(Si2O7)]O22. Batisivite probably pertains to the V 8 3+ Ti 6 4+ [Ba(Si2O)]O28-Cr 8 3+ Ti 6 4+ [Ba(Si2O)]O28 solid solution series. The type material of batisivite has been deposited in the Fersman Mineralogical Museum, Russian Academy of Sciences, Moscow.  相似文献   

19.
The chemical composition of aerosols in the Marine Atmospheric Boundary Layer (MABL) of Bay of Bengal (BoB) and Arabian Sea (AS) has been studied during the spring and inter-monsoon (March-May 2006) based on the analysis of water soluble constituents (Na+, NH 4 + , K+, Mg2+, Ca2+, Cl?, NO 3 ? and SO 4 2? ), crustal elements (Al, Fe, and Ca) and carbonaceous species (EC, OC). The total suspended particulates (TSP) ranged from 5.2 to 46.6 μg m?3 and 8.2 to 46.9 μg m?3 during the sampling transects in the BoB and AS respectively. The water-soluble species, on average, accounted for 44% and 33% of TSP over BoB and AS respectively, with dominant contribution of SO 4 2? over both the oceanic regions. However, distinct differences with respect to elevated abundances of NH 4 + in the MABL of BoB and that of Na+ and Ca2+ in AS are clearly evident. The non-sea-salt component of SO 4 2? ranging from 82 to 98% over BoB and 35 to 98% over AS; together with nss-Ca2+/nss-SO 4 2? equivalent ratios 0.12 to 0.5 and 0.2 to 1.16, respectively, provide evidence for the predominance of anthropogenic constituents and chemical transformation processes occurring within MABL. The concentrations of OC and EC average around 1.9 and 0.4 μg m?3 in BoB and exhibit a decreasing trend from north to south; however, abundance of these carbonaceous species are not significantly pronounced over AS. The abundance of Al, used as a proxy for mineral aerosols, varied from 0.2 to 1.9 μg m?3 over BoB and AS, with a distinctly different spatial pattern — decreasing north to south in BoB in contrast to an increasing pattern in the Arabian Sea.  相似文献   

20.
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