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1.
Solubility curves of water-hydrogen fluid were studied using a high-pressure gas apparatus at a pressure of 200 MPa under
variable fluid composition in haplogranite (Ab
39
Or
32
Qtz
29, 950°C), Na-disilicate (Na2Si2O5, 950°C), and albite melts (1200°C). The mole fraction of hydrogen in experiments was controlled directly by Ar-H2 mixtures using a specially designed cell with a Shaw membrane. $
X_{H_2 }^{Ar - H_2 }
$
X_{H_2 }^{Ar - H_2 }
ranged from 0 to 1. In some experiments with haplogranite and Na-disilicate melts under oxidizing conditions, in order to
increase the accuracy of experimental parameters, the fugacities of oxygen and hydrogen were controlled using the double-capsule
technique and the solid-phase buffer mixtures Ni-NiO (NNO) and Co-CoO (CCO). The addition of H2 to the H2O-saturated systems ($
X_{H_2 }^{H_2 O - H_2 }
$
X_{H_2 }^{H_2 O - H_2 }
≥ 0.012) results in the appearance of a distinct maximum on the solubility curves at $
X_{H_2 }^{H_2 O - H_2 }
$
X_{H_2 }^{H_2 O - H_2 }
= 0.05–0.07 (H2 mole fractions were calculated for real H2O-H2 mixtures of real gases), and the maximum content of H2O-H2 fluid increases relative to the H2O-saturated melts by 1.51 wt % for haplogranite melt at $
X_{H_2 }
$
X_{H_2 }
= 0.063, 2.68 wt % for albite melt at $
X_{H_2 }
$
X_{H_2 }
= 0.066, and 3.54 wt % for Na-disilicate melt at $
X_{H_2 }
$
X_{H_2 }
= 0.067. A further increase in H2 content in the gas mixture decreases the solubility of H2O-H2 fluid in the melts, and under pure H2 pressure, the contents of fluid components are 0.08 wt % in haplogranite melt and 0.06 wt % in albite melt. The 1H NMR study of aluminosilicate and Na-silicate glasses obtained under the pressure of H2O and H2O-H2 fluids suggests different mechanisms of the dissolution of H2O and H2O-H2 fluids in magmatic melts. In addition to the spectra of dissolved water fluid, the spectra of quenched glasses synthesized
under H2O-H2 fluid pressure exhibited a narrow line of molecular hydrogen with a width at half height of 1.8–2.0 kHz at $
X_{H_2 }
$
X_{H_2 }
≥ 0.653 for albite and $
X_{H_2 }
$
X_{H_2 }
≥ 0.063 for Na-disilicate and two lines at $
X_{H_2 }
$
X_{H_2 }
≥ 0.063 for the haplogranite composition. 相似文献
2.
Priscille Lesne Bruno Scaillet Michel Pichavant Giada Iacono-Marziano Jean-Michel Beny 《Contributions to Mineralogy and Petrology》2011,162(1):133-151
Experiments were conducted to determine the water solubility of alkali basalts from Etna, Stromboli and Vesuvius volcanoes,
Italy. The basaltic melts were equilibrated at 1,200°C with pure water, under oxidized conditions, and at pressures ranging
from 163 to 3,842 bars. Our results show that at pressures above 1 kbar, alkali basalts dissolve more water than typical mid-ocean
ridge basalts (MORB). Combination of our data with those from previous studies allows the following simple empirical model
for the water solubility of basalts of varying alkalinity and fO2 to be derived:
\textH 2 \textO( \textwt% ) = \text H 2 \textO\textMORB ( \textwt% ) + ( 5.84 ×10 - 5 *\textP - 2.29 ×10 - 2 ) ×( \textNa2 \textO + \textK2 \textO )( \textwt% ) + 4.67 ×10 - 2 ×\Updelta \textNNO - 2.29 ×10 - 1 {\text{H}}_{ 2} {\text{O}}\left( {{\text{wt}}\% } \right) = {\text{ H}}_{ 2} {\text{O}}_{\text{MORB}} \left( {{\text{wt}}\% } \right) + \left( {5.84 \times 10^{ - 5} *{\text{P}} - 2.29 \times 10^{ - 2} } \right) \times \left( {{\text{Na}}_{2} {\text{O}} + {\text{K}}_{2} {\text{O}}} \right)\left( {{\text{wt}}\% } \right) + 4.67 \times 10^{ - 2} \times \Updelta {\text{NNO}} - 2.29 \times 10^{ - 1} where H2OMORB is the water solubility at the calculated P, using the model of Dixon et al. (1995). This equation reproduces the existing database on water solubilities in basaltic melts to within 5%. Interpretation of
the speciation data in the context of the glass transition theory shows that water speciation in basalt melts is severely
modified during quench. At magmatic temperatures, more than 90% of dissolved water forms hydroxyl groups at all water contents,
whilst in natural or synthetic glasses, the amount of molecular water is much larger. A regular solution model with an explicit
temperature dependence reproduces well-observed water species. Derivation of the partial molar volume of molecular water using
standard thermodynamic considerations yields values close to previous findings if room temperature water species are used.
When high temperature species proportions are used, a negative partial molar volume is obtained for molecular water. Calculation
of the partial molar volume of total water using H2O solubility data on basaltic melts at pressures above 1 kbar yields a value of 19 cm3/mol in reasonable agreement with estimates obtained from density measurements. 相似文献
3.
Mineral-specific IR absorption coefficients were calculated for natural and synthetic olivine, SiO2 polymorphs, and GeO2 with specific isolated OH point defects using quantitative data from independent techniques such as proton–proton scattering,
confocal Raman spectroscopy, and secondary ion mass spectrometry. Moreover, we present a routine to detect OH traces in anisotropic
minerals using Raman spectroscopy combined with the “Comparator Technique”. In case of olivine and the SiO2 system, it turns out that the magnitude of ε for one structure is independent of the type of OH point defect and therewith
the peak position (quartz ε = 89,000 ± 15,000
\textl \textmol\textH2\textO-1 \textcm-2\text{l}\,\text{mol}_{{\text{H}_2}\text{O}}^{-1}\,\text{cm}^{-2}), but it varies as a function of structure (coesite ε = 214,000 ± 14,000
\textl \textmol\textH2\textO-1 \textcm-2\text{l}\,\text{mol}_{{\text{H}_2}\text{O}}^{-1}\,\text{cm}^{-2}; stishovite ε = 485,000 ± 109,000
\textl \textmol\textH2\textO-1 \textcm-2\text{l}\,\text{mol}_{{\text{H}_2}\text{O}}^{-1}\,\text{cm}^{-2}). Evaluation of data from this study confirms that not using mineral-specific IR calibrations for the OH quantification in
nominally anhydrous minerals leads to inaccurate estimations of OH concentrations, which constitute the basis for modeling
the Earth’s deep water cycle. 相似文献
4.
The solubility of pentatungstate of sodium (PTS) Na2W5O16 · H2O and sodium tungsten bronzes (STB) Na0.16WO3 in acid chloride solutions containing 0.026, 0.26, and 3.02m NaCl have been studied at 500°C, 1000 bar, given fO2 (Co-CoO, Ni-NiO, PTS-STB buffers), and constant NaCl/HCl ratio (Ta2O5-Na2Ta4O11 buffer). Depending on experimental conditions, the tungsten content in the solutions after experiments varied from 10−3 to 2 × 10−2 mol/kg H2O. Obtained data were used to calculate the formation constants of predominant tungsten complexes (VI, V): H3W3VIO123−, W3VO93−, [WVW4VIO16]3−, for reactions
|
$
\begin{gathered}
3H_2 WO_4^0 \leftrightarrow H_3 W_3 O_{12}^{3 - } + 3H^ + \log K_p = - 7.5 \pm 0.1, \hfill \\
3H_2 WO_4^0 \leftrightarrow W_3 O_9^{3 - } + 1.5H_2 O + 3H^ + + 0.75O_2 \log K_p = - 25.7 \pm 0.2, \hfill \\
5H_2 WO_4^0 \leftrightarrow \left[ {W^V W_4^{VI} O_{16} } \right]^{3 - } + 3H^ + + 3.5H_2 O + 0.25O_2 \log K_p = - 4.6 \pm 0.1 \hfill \\
\end{gathered}
$
\begin{gathered}
3H_2 WO_4^0 \leftrightarrow H_3 W_3 O_{12}^{3 - } + 3H^ + \log K_p = - 7.5 \pm 0.1, \hfill \\
3H_2 WO_4^0 \leftrightarrow W_3 O_9^{3 - } + 1.5H_2 O + 3H^ + + 0.75O_2 \log K_p = - 25.7 \pm 0.2, \hfill \\
5H_2 WO_4^0 \leftrightarrow \left[ {W^V W_4^{VI} O_{16} } \right]^{3 - } + 3H^ + + 3.5H_2 O + 0.25O_2 \log K_p = - 4.6 \pm 0.1 \hfill \\
\end{gathered}
相似文献
5.
M. Zhang G. J. Redhammer E. K. H. Salje M. Mookherjee 《Physics and Chemistry of Minerals》2002,29(9):609-616
Synthetic aegirine LiFeSi2O6 and NaFeSi2O6 were characterized using infrared spectroscopy in the frequency range 50–2000 cm−1, and at temperatures between 20 and 300 K. For the C2/c phase of LiFeSi2O6, 25 of the 27 predicted infrared bands and 26 of 30 predicted Raman bands are recorded at room temperature. NaFeSi2O6 (with symmetry C2/c) shows 25 infrared and 26 Raman bands. On cooling, the C2/c–P21/c structural phase transition of LiFeSi2O6 is characterized by the appearance of 13 additional recorded peaks. This observation indicates the enlargement of the unit
cell at the transition point. The appearance of an extra band near 688 cm−1 in the monoclinic P21/c phase, which is due to the Si–O–Si vibration in the Si2O6 chains, indicates that there are two non-equivalent Si sites with different Si–O bond lengths. Most significant spectral
changes appear in the far-infrared region, where Li–O and Fe–O vibrations are mainly located. Infrared bands between 300 and
330 cm−1 show unusually dramatic changes at temperatures far below the transition. Compared with the infrared data of NaFeSi2O6 measured at low temperatures, the change in LiFeSi2O6 is interpreted as the consequence of mode crossing in the frequency region. A generalized Landau theory was used to analyze
the order parameter of the C2/c–P21/c phase transition, and the results suggest that the transition is close to tricritical.
Received: 21 January 2002 / Accepted: 22 July 2002 相似文献
6.
We present results from low-temperature heat capacity measurements of spinels along the solid solution between MgAl2O4 and MgCr2O4. The data also include new low-temperature heat capacity measurements for MgAl2O4 spinel. Heat capacities were measured between 1.5 and 300 K, and thermochemical functions were derived from the results.
No heat capacity anomaly was observed for MgAl2O4 spinel; however, we observe a low-temperature heat capacity anomaly for Cr-bearing spinels at temperatures below 15 K. From
our data we calculate standard entropies (298.15 K) for Mg(Cr,Al)2O4 spinels. We suggest a standard entropy for MgAl2O4 of 80.9 ± 0.6 J mol−1 K−1. For the solid solution between MgAl2O4 and MgCr2O4, we observe a linear increase of the standard entropies from 80.9 J mol−1 K−1 for MgAl2O4 to 118.3 J mol−1 K−1 for MgCr2O4. 相似文献
7.
The diffusion of water in a peralkaline and a peraluminous rhyolitic melt was investigated at temperatures of 714–1,493 K
and pressures of 100 and 500 MPa. At temperatures below 923 K dehydration experiments were performed on glasses containing
about 2 wt% H2O
t
in cold seal pressure vessels. At high temperatures diffusion couples of water-poor (<0.5 wt% H2O
t
) and water-rich (~2 wt% H2O
t
) melts were run in an internally heated gas pressure vessel. Argon was the pressure medium in both cases. Concentration profiles
of hydrous species (OH groups and H2O molecules) were measured along the diffusion direction using near-infrared (NIR) microspectroscopy. The bulk water diffusivity
() was derived from profiles of total water () using a modified Boltzmann-Matano method as well as using fittings assuming a functional relationship between and Both methods consistently indicate that is proportional to in this range of water contents for both bulk compositions, in agreement with previous work on metaluminous rhyolite. The
water diffusivity in the peraluminous melts agrees very well with data for metaluminous rhyolites implying that an excess
of Al2O3 with respect to alkalis does not affect water diffusion. On the other hand, water diffusion is faster by roughly a factor
of two in the peralkaline melt compared to the metaluminous melt. The following expression for the water diffusivity in the
peralkaline rhyolite as a function of temperature and pressure was obtained by least-squares fitting:
8.
L. M. Chechin 《Astronomy Reports》2010,54(8):719-723
The rotational effect of the cosmic vacuum is investigated. The induced rotation of elliptical galaxies due to the anti-gravity
of the vacuum is found to be 10−21 s−1 for real elliptical galaxies. The effect of the vacuum rotation of the entire Universe is discussed, and can be described
by the invariant ω
ν
= ω
0 ∼ $
\sqrt {G\rho v}
$
\sqrt {G\rho v}
. The corresponding numerical angular velocity of the Universe is 10−19 s−1, in good agreement with modern data on the temperature fluctuations of the cosmic background radiation. 相似文献
9.
Summary The complexation of aluminium(III) and silicon(IV) was studied in a simplified seawater medium (0.6 M Na(Cl)) at 25 °C. The
measurements were performed as potentiometric titrations using a hydrogen electrode with OH
− ions being generated coulometrically. The total concentrations of Si(IV) and Al(III) respectively [Si
tot
] and [Al
t
ot], and −log[H
+] were varied within the limits 0.3 < [Si
tot
] < 2.5 mM, 0.5 < [Al
tot
] < 2.6 mM, and 2 ≤ -log[H
+] ≤ 4.2. Within these ranges of concentration, evidence is given for the formation of an AlSiO(OH)
3
2+
complex with a formation constant log β1,1-1 = −2.75 ± 0.1 defined by the reaction
Al
3++Si (OH)4 ↔ AlOSi(OH)
3
2+
+H
+
An extrapolation of this value to I=0 gives log β1,1-1 = −2.30. The calculated value of log K (Al
3++SiO(OH)
3
−
↔ AlOSi(OH)
3
2+
) = 6.72 (I=0.6 M) can be compared with corresponding constants for the formation of AlF
2+ and AlOH
2+ , which are equal to 6.16 and 8.20. Obviously, the stability of these Al(III) complexes decreases within the series OH
−>SiO(OH)
3
−
> F
− 相似文献
10.
The redox state of the continental lithospheric mantle of the Baikal-Mongolia region 总被引：1，自引：0，他引：1
L. P. Nikitina A. G. Goncharov A. K. Saltykova M. S. Babushkina 《Geochemistry International》2010,48(1):15-40
The thermal and redox state of the upper mantle beneath the Baikal-Mongolia region was estimated on the basis of the investigation
of the chemical composition (including iron oxidation state) of major minerals (olivine, orthopyroxene, clinopyroxene, and
spinel) in spinel and garnet-spinel peridotite xenoliths from the Cenozoic alkali basalts of the volcanic fields of the Dariganga
Plateau, Tariat Depression, and Vitim Plateau. At temperatures of 1030–1500°C and pressures of 29–47 kbar, the Δlog$
f_{O_2 }
$
f_{O_2 }
values relative to the FMQ buffer (calculated using the olivine-spinel oxygen barometer) range from −0.9 to −1.7 for the
xenoliths of the Dariganga Plateau, from −0.9 to −1.8 for the Tariat Depression, and from −0.8 to −0.1 for the Vitim Plateau.
The oxygen fugacity of peridotites from all of the areas is, in general, lower than that of the WM buffer. Oxygen fugacity
is usually below the CCO and EMOD/G buffers in the peridotites of the Dariganga Plateau and the Tariat Depression and higher
than these buffers in the peridotites of the Vitim Plateau. The T-PΔlog$
f_{O_2 }
$
f_{O_2 }
relationships in the xenoliths suggest the existence of spatial heterogeneity in the thermal and redox state of the upper
mantle of the Baikal-Mongolia region. This heterogeneity is probably related to the influence of the plume that was responsible
for the Late Mesozoic-Cenozoic intraplate magmatism of this region and reflects the different distance of the respective mantle
domains from the plume head. The C-O-H fluids in equilibrium with the upper mantle peridotites are composed mainly of water
and carbon dioxide. The mantle of the Dariganga Plateau and the Tariat Depression (Δlog$
f_{O_2 }
$
f_{O_2 }
< −0.9) is characterized by the dominance of H2O, whereas CO2-rich fluids are characteristic of the more oxidized mantle of the Vitim Plateau (Δlog$
f_{O_2 }
$
f_{O_2 }
is mostly higher than −0.8). 相似文献
11.
The stability and the thermo-elastic behaviour of a natural londonite
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