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1.
The spatial structure of the metal-poor globular cluster M15 is studied as a function of magnitude interval ΔB and the limiting B magnitude of star counts. Astrometric and photometric measurements of two plates obtained with the 2-m reflector of the National Academy of Sciences of Bulgaria were used. Analysis of the differential and integrated apparent (ΔF(r) and F(r)) and spatial (Δf(r) and f(r)) stellar density distributions in different ΔB intervals and to different limiting magnitudes reaching B=21.5m indicates that the cluster structure changes systematically as we consider fainter stars, beginning with the transition region between the subgiant branch and the main-sequence turnoff in the (V, B-V) diagram. This variation is manifest in two ways: a homological growth in the radii of spatial zones of the cluster and of the cluster radius in accordance with a single law, and variations in the stellar density, with the rate of increase in the number of faint stars growing toward the outer zones of the cluster. Empirical relations describing these variations and parameters determining the cluster structure are obtained.  相似文献   

2.
Lower limits for the percentages of stars with various luminosities in the cores of six globular clusters are derived using stellar spatial density distributions f(r) to deep limiting B magnitudes obtained earlier. For NGC 6535 and NGC 5466, the logarithmic density range and Kholopov parameters Df and Dr are also determined. These two parameters are correlated with the mean masses of stars of various subsystems and the total mass (number) of stars in the cluster.  相似文献   

3.
Molecular orbital calculations on a variety of silicate and aluminosilicate molecules have been used to explore the bonding forces that govern tetrahedral bond length variations, r(TO), in framework silicates and aluminosilicates. Not only do the calculations provide insight into the variety of structural types and the substitution limits of one tetrahedral atom for another, but they also provide an understanding of the interrelationships among r(TO) and linkage factors, bond strength sum, coordination number, and angles within and between tetrahedra. A study of these interrelationships for a theoretical data set shows that r(SiO) and r(AlO) are linearly correlated with (1) p o, the bond strength sum to a bridging oxygen, (2) f s(O), the fractional s-character of a bridging oxygen, and (3) f s (T), the fractional s-character of the T atom. In a multiple linear regression analysis of the data, 92% of the variation of r(SiO) and 99% of the variation of r(AlO) can be explained in terms of a linear dependence on p o, f s (O), and f s (T). Analogous regression analyses completed for observed r(Al, SiO) bond length data from a number of silica polymorphs and ordered aluminosilicates account for more than 75% of the bond length variation. The lower percentage of bond length variation explained is ascribed in part to the random and systematic errors in the experimental data which have a negligible effect on the theoretical data. The modeling of more than 75% of the variation of r(Al, SiO) in the framework silicates using the same model used for silicate and aluminosilicate molecules strengthens the viewpoint that the bonding forces that govern the shapes of such molecules are quite similar to the forces that govern the shapes of chemically similar groups in solids. The different regression coefficients calculated for f s (T) indicate that SiO and AlO bond length variations in framework structures should not be treated as a single population in estimating the average Al, Si content of a tetrahedral site.  相似文献   

4.
Given ri =f i(F) andK i = gi(F), wherer i is the mineral mass fraction in an instantaneous solid phase,K i the partition coefficient, andf i(F) andg i(F) respectively the continuous, sectionally smooth functions of solidification degreeF, we have: $$C^1 = \frac{{C_0 }}{{1 - F}} \cdot \exp \left( { - \int_0^F {\frac{{\Sigma fi(F) \cdot g_i (F)}}{{1 - F}} \cdot dF} } \right)and \bar C^s = \frac{{C_o }}{F}\left[ {1 - (1 - F) \cdot \frac{{C^1 }}{{C^0 }}} \right]$$ Also presented in this paper are other equations describing the compositional changes of solid and liquid phases in magmatic processes (partial melting). The following understanding is attained based on the application of these equations to the Hushan pluton of Mt. Taishan in the west of Shandong Province. 1) For granitoids changes in rock-forming minerals may not be taken into consideration in theoretical modelling of REE distribution, but accessory minerals rich in REE, especially those highly rich in some REE must be taken into account. 2) In the case of well differentiated granitoids, it can be assumed thatFε [0,1] may exert only little influence on the calculations. 3) In practice the (La / Sm)-La diagram should be applied with care.  相似文献   

5.
We have modeled the magnetic fields of the slowly rotating stars HD 116458 and HD 126515 using the “magnetic charge” technique. HD 116458 has a small angle between its rotation axis and dipole axis (β = 12°), whereas this angle is large for HD 126515 (β = 86°). Both stars can be described with a decentered-dipole model, with the respective displacements being r = 0.07 and r = 0.24 in units of the stellar radius. The decentered-dipole model is able to satisfactorily explain the phase relations for the effective field, Be(P), and the mean surface field, Bs(P), for both stars, along with the fact that the Be(P) phase relation for HD 126515 is anharmonic. We discuss the role of systematic measurement errors possibly resulting from instrumental or methodical effects in one or both of the phase relations. The displacement of the dipole probably reflects real asymmetry of the stellar field structure, and is not due to measurement errors. Using both phase relations, Be(P) and Bs(P), in the modeling considerably reduces the influence of the nonuniform distribution of chemical elements on the stellar surface.  相似文献   

6.
Measurements of the dissolution rate of diopside (r) were carried out as a function of the Gibbs free energy of the dissolution reaction (ΔGr) in a continuously stirred flow-through reactor at 90 °C and pH90 °C = 5.05. The overall relation between r and ΔGr was determined over a free energy range of −130.9 < ΔGr < −47.0 kJ mo1−1. The data define a highly non-linear, sigmoidal relation between r and ΔGr. At far-from-equilibrium conditions (ΔGr ? −76.2 kJ mo1−1), a rate plateau is observed. In this free energy range, the rates of dissolution are constant, independent of [Ca], [Mg] and [Si] concentrations, and independent of ΔGr. A sharp decrease of the dissolution rate (∼1 order of magnitude) occurs in the transition ΔGr region defined by −76.2 < ΔGr ? −61.5 kJ mo1−1. Dissolution closer to equilibrium (ΔGr > −61.5 kJ mo1−1) is characterised by a much weaker inverse dependence of the rates on ΔGr. Modeling the experimental r-ΔGr data with a simple classical transition state theory (TST) law as implemented in most available geochemical codes is found inappropriate. An evaluation of the consequences of the use of geochemical codes where the r-ΔGr relation is based on basic TST was carried out and applied to carbonation reactions of diopside, which, among other reactions with Ca- and Mg-bearing minerals, are considered as a promising process for the solid state sequestration of CO2 over long time spans. In order to take into account the actual experimental r-ΔGr relation in the geochemical code that we used, a new module has been developed. It reveals a dramatic overestimation of the carbonation rate when using a TST-based geochemical code. This points out that simulations of water-rock-CO2 interactions performed with classical geochemical codes should be evaluated with great caution.  相似文献   

7.
We have used published, high-accuracy, ground-based and satellite proper-motion measurements, a compilation of radial velocities, and photometric distances to compute the spatial velocities and Galactic orbital elements for 174 RR Lyrae (ab) variable stars in the solar neighborhood. The computed orbital elements and published heavy-element abundances are used to study relationships between the chemical, spatial, and kinematic characteristics of nearby RR Lyrae variables. We observe abrupt changes of the spatial and kinematic characteristics at the metallicity [Fe/H]≈?0.95 and also when the residual spatial velocities relative to the LSR cross the critical value V res≈290 km/s. This provides evidence that the general population of RR Lyrae stars is not uniform and includes at least three subsystems occupying different volumes in the Galaxy. Based on the agreement between typical parameters for corresponding subsystems of RR Lyrae stars and globular clusters, we conclude that metal-rich stars and globular clusters belong to a rapidly rotating and fairly flat, thick-disk subsystem with a large negative vertical metallicity gradient. Objects with larger metal deficiencies can, in turn, be subdivided into two populations, but using different criteria for stars and clusters. We suggest that field stars with velocities below the critical value and clusters with extremely blue horizontal branches form a spherical, slowly rotating subsystem of the protodisk halo, which has a common origin with the thick disk; this subsystem has small but nonzero radial and vertical metallicity gradients. The dimensions of this subsystem, estimated from the apogalactic radii of orbits of field stars, are approximately the same. Field stars displaying more rapid motion and clusters with redder horizontal branches constitute the spheroidal subsystem of the accreted outer halo, which is approximately a factor of three larger in size than the first two subsystems. It has no metallicity gradients; most of its stars have eccentric orbits, many display retrograde motion in the Galaxy, and their ages are comparatively low, supporting the hypothesis that the objects in this subsystem had an extragalactic origin.  相似文献   

8.
In dynamical models for open clusters, virial equilibrium is not achieved over the violent relaxation time scale τvr. The stars form an equilibrium distribution in (?, ?ζ, l) space, where ? and l are the energy and angular momentum per unit stellar mass in the combined field of the Galaxy and cluster and ?ζ is the energy of motion perpendicular to the Galactic plane per unit mass of cluster stars in the gravitational field of the Galaxy. This distribution of stars changes little when t>τvr. The stellar phase-space distribution corresponding to this type of equilibrium and the regular cluster potential vary periodically (or quasi-periodically) with time. This phase-space equilibrium is probably possible due to an approximate balance in the stellar transitions between phase-space cells over times equal to the oscillation period for the regular cluster field.  相似文献   

9.
The thermochemistry of well-characterized synthetic K-H3O, Na-H3O and K-Na-H3O jarosites was investigated. These phases are solid solutions that obey Vegard’s law. Electron probe microanalyses indicated lower alkali and iron contents than predicted from the theoretical end-member compositions, in agreement with thermal analyses, suggesting the presence of hydronium and “additional” water. The standard enthalpies of formation (ΔH°f) of K-H3O, Na-H3O and K-Na-H3O jarosites were determined by high-temperature oxide melt solution calorimetry. These enthalpies vary linearly with the K/H3O, Na/H3O and K/Na ratio, respectively. The enthalpy of formation of pure hydronium jarosite was also determined experimentally (ΔH°f = −3741.6 ± 8.3 kJ.mol−1), and it was used to evaluate ΔH°f for the end-members KFe3(SO4)2(OH)6 (ΔH°f = −3829.6 ± 8.3 kJ.mol−1) and NaFe3(SO4)2(OH)6 (ΔH°f = −3783.4 ± 8.3 kJ.mol−1). Finally, enthalpies of dehydration (loss of the “additional” water) of some jarosites were determined and found to be near the enthalpy of vaporization of water, suggesting that the “additional” water is weakly bonded in the structure.  相似文献   

10.
Pore waters of natural clays, which are investigated as potential host rock formations for high-level nuclear waste, are known to contain large amounts of low-molecular weight organic compounds. These small organic ligands might impact the aqueous geochemistry of the stored radionuclides and, thus, their migration behavior. In the present work, the complexation of Cm(III) with formate in aqueous NaCl solution is investigated by time-resolved laser fluorescence spectroscopy (TRLFS) as a function of the ionic strength (0.5–3.0 mol/kg), the ligand concentration (0–0.2 mol/kg) and the temperature (20–90 °C). The Cm(III) speciation is determined by deconvolution of the emission spectra. The obtained distribution of Cm(III) species is used to calculate the conditional stability constants (log K′(T)) at a given temperature and ionic strength which are extrapolated to zero ionic strength by using the specific ion interaction theory (SIT). Thus, the thermodynamic log K0n(T) values for the formation of [Cm(Form)n](3−n)+ (n = 1, 2) and the ion interaction coefficients (ε(i,k)) for [Cm(Form)n](3−n)+ (n = 1, 2) with Cl− are obtained. The log K01(T) (2.11 (20 °C)–2.49 (90 °C)) and log K02(T) values (1.17 (30 °C–2.01 (90 °C)) increase continuously with increasing temperature. The log K0n(T) values are used to derive the standard reaction enthalpies and entropies (ΔrH0m, ΔrS0m) of the respective complexation reactions according to the Van’t Hoff equation. In all cases, positive ΔrH0m and ΔrS0m values are obtained. Thus, both complexation steps are endothermic and entropy-driven.  相似文献   

11.
The instability of transition metal dolomites [CaR2+(CO3)2 where R2+ is Fe, Co, Ni, Cu, or Zn] and the limited substitution of transition metal cations for Mg in the dolomite structure can be accounted for by the effect of octahedral distortion. For example, trigonal elongation of the Fe octahedron, due to the Jahn-Teller effect, observed in siderite and ankerite, results in elongation of the Ca octahedron which is sensitive to distortion because the radius of Ca2+ is close to the upper limit for octahedral coordination. Co, Ni, Cu, Zn octahedra are also thought to be deformed, relative to Mg octahedra, in carbonates.The free energy of formation (ΔGof) of R2+CO3 becomes more positive with increasing octahedral distortion. Estimated ΔGof(dolomite) as well as stabilities and solubility limits of R2+ in natural and synthetic dolomites suggest a series in order of decreasing stability: Mg >Mn >Zn >Fe >Co >Ni >Cu.ΔGof(est.) for the terminal Fe-dolomite solid solution [72 mol% CaFe(CO3)2] in the system CaCO3-MgCO3-FeCO3 may represent an empirical threshold value for dolomite stability which lies between ΔGof for Mn- and Zn-dolomites. While Zn-dolomite is probably not a stable phase, very extensive solid solution toward CaZn(CO3)2 is to be expected in the system CaCO3-MgCO3-ZnCO3. The tendency for transition metal dolomites to contain excess CaCO3 can also be accounted for in terms of octahedral distortion and AGof.  相似文献   

12.
Partition coefficients (K) between forsterite crystal and melt are experimentally determined for many univalent, bivalent, trivalent, and tetravalent trace elements. Using numerical modeling, we calculated the energies of intrinsic and impurity defects in forsterite (E df) and the energies of dissolution of univalent, bivalent, trivalent, and tetravalent impurities (E ds). These results are compared with literature data. A linear dependence is established for the energy of defects on the charge of the impurity ion and the relative difference in the radii of the impurity and matrix ions Δr/d, where d is the average interatomic distance in the matrix. Partition coefficients are described by parabolic dependences on Δr/d and charge of the impurity ion using literature data on K of impurity elements in olivines and impurity ion dissolution energies. Linear dependences-RTlnK-(Δr/d)2 and E ds-(Δr/d)2 pass through the origin for isovalent substitutions and are well apart from it for heterovalent substitutions. Linear dependence (Δr/d)2 has a free term of about 200 kJ/mol, which is approximately equal to a half of the energy of formation of the Frenkel defect in forsterite; this defect maintains electroneutrality. If valency is compensated due to addition into the melt of an ion with another charge (than that of the impurity ion), E ds-(Δr/d)2 and-RTlnK-(Δr/d)2 lines at low (Δr/d)2 shift to the origin. This means that energy consumption for coupled isomorphism is lower than that for the formation of intrinsic structural defects. Correlation dependences are proposed for the distribution of impurities and the energy of their dissolution. They indicate the increasing contribution of the entropy components of impurity ion dissolution energy during heterovalent isomorphism.  相似文献   

13.
Albrechtschraufite, MgCa4F2[UO2(CO3)3]2?17-18H2O, triclinic, space group Pī, a?=?13.569(2), b?=?13.419(2), c?=?11.622(2) Å, α?=?115.82(1), β?=?107.61(1), γ?=?92.84(1)° (structural unit cell, not reduced), V?=?1774.6(5) Å3, Z?=?2, D c?=?2.69 g/cm3 (for 17.5 H2O), is a mineral that was found in small amounts with schröckingerite, NaCa3F[UO2(CO3)3](SO4)?10H2O, on a museum specimen of uranium ore from Joachimsthal (Jáchymov), Czech Republic. The mineral forms small grain-like subhedral crystals (≤ 0.2 mm) that resemble in appearance liebigite, Ca2[UO2(CO3)3]??~?11H2O. Colour pale yellow-green, luster vitreous, transparent, pale bluish green fluorescence under ultraviolet light. Optical data: Biaxial negative, nX?=?1.511(2), nY?=?1.550(2), nZ?=?1.566(2), 2?V?=?65(1)° (λ?=?589 nm), r < v weak. After qualitative tests had shown the presence of Ca, U, Mg, CO2 and H2O, the chemical formula was determined by a crystal structure analysis based on X-ray four-circle diffractometer data. The structure was later on refined with data from a CCD diffractometer to R1?=?0.0206 and wR2?=?0.0429 for 9,236 independent observed reflections. The crystal structure contains two independent [UO2(CO3)3]4? anions of which one is bonded to two Mg and six Ca while the second is bonded to only one Mg and three Ca. Magnesium forms a MgF2(Ocarbonate)3(H2O) octahedron that is linked via the F atoms with three Ca atoms so as to provide each F atom with a flat pyramidal coordination by one Mg and two Ca. Calcium is 7- and 8-coordinate forming CaFO6, CaF2O2(H2O)4, CaFO3(H2O)4 and CaO2(H2O)6 coordination polyhedra. The crystal structure is built up from MgCa3F2[UO2(CO3)3]?8H2O layers parallel to (001) which are linked by Ca[UO2(CO3)3]?5H2O moieties into a framework of the composition MgCa4F2[UO2(CO3)3]?13H2O. Five additional water molecules are located in voids of the framework and show large displacement parameters. One of the water positions is partly vacant, leading to a total water content of 17-18H2O per formula unit. The MgCa3F2[UO2(CO3)3]?8H2O layers are pseudosymmetric according to plane group symmetry cmm. The remaining constituents do not sustain this pseudosymmetry and make the entire structure truly triclinic. A characteristic paddle-wheel motif Ca[UO2(CO3)3]4Ca relates the structure of albrechtschraufite partly to that of andersonite and two synthetic alkali calcium uranyl tricarbonates.  相似文献   

14.
We have modeled the Hα, Hβ, and Hγ (Balmer series), P14 (Paschen series), and Brγ (Brackett series) hydrogen lines formed in the inner regions of the accretion disk around the Herbig Ae star UX Ori. Our calculations are based on spectra obtained with the Nordic Optical Telescope (NOT) and the IRTF. We computed a grid of non-LTE models for a radiating area in the accretion disk and determined the basic parameters of the lines using the method of Sobolev. Analyzing the theoretical and observed line profiles, equivalent widths, and luminosities, we have estimated the accretion rate and electron-temperature distribution in the inner parts of the accretion disk. The accretion rate of UX Ori is about $\dot M_a = (3 - 10) \times 10^{ - 9} M_ \odot /yr$ , and the temperature distribution is consistent with the power law T(r)=T(r *)(r/r *)?1/n , where the electron temperature near the stellar surface T(r *) is 15000–20000 K and the power-law index n≈2–3 is about two to three. The resulting value for $\dot M_a $ eliminates problems connected with the application of magnetospheric accretion models to Herbig Ae/Be stars. Another important conclusion is that, at the estimated accretion rate, the energy release is substantially (about two orders of magnitude) lower than the stellar luminosity. Therefore, the optical radiation of UX Ori accretion disks cannot appreciably contribute to the observed variability of these stars, which must be determined mainly by variability in the circumstellar extinction.  相似文献   

15.
The parameters of the quadruple system ADS 9626 (µ Boo) are analyzed. The system consists of two double stars: the Aa pair with an angular separation of ρ = 0.08″ and the BC pair with an angular separation of ρ = 2.2″, separated by ρ = 107″ and having the same parallaxes and proper motions. Position observations with the Pulkovo 26″ refractor have yielded from direct astrometric measurements the difference in the apparent magnitudes and the component-mass ratio for the BC subsystem: Δm = 0.59 ± 0.06, M(B)/M(C) = 1.18 ± 0.02. Spectroscopy with the Russian-Turkish 1.5-m telescope has yielded the radial velocities and physical parameters of the Aa, B, and C components. Speckle-interferometric observations with the 6-m telescope of the Special Astrophysical Observatory have provided the first measurements of the magnitude difference in the close Aa subsystem: Δm = 0.46 ± 0.03 (λ = 5500 Å) and Δm = 0.41 ± 0.03 (λ = 8000 Å). The new observations are consistent with the known orbits, which were used to find the radial velocities for the centers of mass of the inner subsystems. Themotion of the outer pair, Aa-BC, is studied using the apparent motion parameters (AMP) method. It is not possible to derive an elliptical orbit for this pair; the elements of a hyperbolic orbit have been estimated. The difference of the heavy-element abundances for the Aa and BC subsystems of 0.5 dex confirms that these pairs have a different origin. This suggests that we are observing here a close encounter of two binary stars.  相似文献   

16.
The two most abundant network-modifying cations in magmatic liquids are Ca2+ and Mg2+. To evaluate the influence of melt structure on exchange of Ca2+ and Mg2+ with other geochemically important divalent cations (m-cations) between coexisting minerals and melts, high-temperature (1470-1650 °C), ambient-pressure (0.1 MPa) forsterite/melt partitioning experiments were carried out in the system Mg2SiO4-CaMgSi2O6-SiO2 with ?1 wt% m-cations (Mn2+, Co2+, and Ni2+) substituting for Ca2+ and Mg2+. The bulk melt NBO/Si-range (NBO/Si: nonbridging oxygen per silicon) of melt in equilibrium with forsterite was between 1.89 and 2.74. In this NBO/Si-range, the NBO/Si(Ca) (fraction of nonbridging oxygens, NBO, that form bonds with Ca2+, Ca2+-NBO) is linearly related to NBO/Si, whereas fraction of Mg2+-NBO bonds is essentially independent of NBO/Si. For individual m-cations, rate of change of KD(m−Mg) with NBO/Si(Ca) for the exchange equilibrium, mmelt + Mgolivine ? molivine + Mgmelt, is linear. KD(m−Mg) decreases as an exponential function of increasing ionic potential, Z/r2 (Z: formal electrical charge, r: ionic radius—here calculated with oxygen in sixfold coordination around the divalent cations) of the m-cation. The enthalpy change of the exchange equilibrium, ΔH, decreases linearly with increasing Z/r2 [ΔH = 261(9)-81(3)·Z/r2 (Å−2)]. From existing information on (Ca,Mg)O-SiO2 melt structure at ambient pressure, these relationships are understood by considering the exchange of divalent cations that form bonds with nonbridging oxygen in individual Qn-species in the melts. The negative ∂KD(m−Mg)/∂(Z/r2) and ∂(ΔH)/∂(Z/r2) is because increasing Z/r2 is because the cations forming bonds with nonbridging oxygen in increasingly depolymerized Qn-species where steric hindrance is decreasingly important. In other words, principles of ionic size/site mismatch commonly observed for trace and minor elements in crystals, also govern their solubility behavior in silicate melts.  相似文献   

17.
We have determined the Nd3+ diffusion kinetics in natural enstatite crystals as a function of temperature, f(O2) and crystallographic direction at 1 bar pressure and applied these data to several terrestrial and planetary problems. The diffusion is found to be anisotropic with the diffusion parallel to the c-axial direction being significantly greater than that parallel to a- and b-axis. Also, D(//a) is likely to be somewhat greater than D(//b). Diffusion experiments parallel to the b-axial direction as a function of f(O2) do not show a significant dependence of D(Nd3+) on f(O2) within the range defined by the IW buffer and 1.5 log unit above the WM buffer. The observed diffusion anisotropy and weak f(O2) effect on D(Nd3+) may be understood by considering the crystal structure of enstatite and the likely diffusion pathways. Using the experimental data for D(Nd3+), we calculated the closure temperature of the Sm-Nd geochronological system in enstatite during cooling as a function of cooling rate, grain size and geometry, initial (peak) temperature and diffusion direction. We have also evaluated the approximate domain of validity of closure temperatures calculated on the basis of an infinite plane sheet model for finite plane sheets showing anisotropic diffusion. These results provide a quantitative framework for the interpretation of Sm-Nd mineral ages of orthopyroxene in planetary samples. We discuss the implications of our experimental data to the problems of melting and subsolidus cooling of mantle rocks, and the resetting of Sm-Nd mineral ages in mesosiderites. It is found that a cooling model proposed earlier [Ganguly J., Yang H., Ghose S., 1994. Thermal history of mesosiderites: Quantitative constraints from compositional zoning and Fe-Mg ordering in orthopyroxene. Geochim. Cosmochim. Acta 58, 2711-2723] could lead to the observed ∼90 Ma difference between the U-Pb age and Sm-Nd mineral age for mesosiderites, thus obviating the need for a model of resetting of the Sm-Nd mineral age by an “impulsive disturbance” [Prinzhoffer A, Papanastassiou D.A, Wasserburg G.J., 1992. Samarium-neodymium evolution of meteorites. Geochim. Cosmochim. Acta 56, 797-815].  相似文献   

18.
From conductance measurements, the negative logarithm of the dissociation constant of the CaHCO3+ ion pair, pK(CaHCO3+), is 0.7, 1.0 and 1.35 within ±0.05 units at 0, 25 and 60°C, respectively. A revaluation of published and unpublished data yields pK(CaCO30) ≈ 3.2 at 25°C. Use of these pK's to compute the dissociation constant of calcite (Kc) from published calcite solubility measurements in pure water gives pKc values which increase markedly with ionic strength. However, if the ion pairs are ignored, computed pKc values are nearly constant with ionic strength. All reasonable attempts to eliminate the trend in pKc by adjusting ion activity coefficients, and/or values of K(CaCO30) failed, so the dilemma remains. Kc values computed from the most reliable published calcite solubility data are in good agreement with such values based on solubility data measured in this study at 5, 15, 35 and 50°C. Study results ignoring ion pairs are accurately represented by the equation log Kc = 13.870 — (3059/T) ?0.04035T, and correspond to ?8.35, ?8.42, and ?8.635 at 0, 25 and 50°C, respectively. The logarithmic expression leads to ΔHro = ?2420 ± 300 cal/mol, ΔCp = ?110 ± 2 cal/deg mol, and ΔSro = ?46.6 ± 1.0 cal/deg mol for the calcite dissociation reaction at 25°C. The dependence of Kc on temperature when CaCO30 and CaHCO3+ are assumed, is described by log Kc = 13.543 ? (3000/T) ? 0.0401T which yields ?8.39, ?8.47, and -8.70 at 0, 25 and 50°C. This gives ΔHro = ?2585 ± 300 cal/mol, ΔCp = ?109 ± 2 cal/deg mol, and ΔSr0 = ?47.4 ± 1.0 cal/deg mol at 25°C.  相似文献   

19.
Mössbauer studies of micas on the polylithionite-side-rophyllite join show the existence of a relation between the quadrupole splitting (ΔE Q) values of Fe2+ high spin doublets and both cationic and anionic composition of micas. This linear relation is positive as Li2O content increases and negative as F content increases. In the lithium iron micas, the inner ferrous quadrupole doublet is assigned to the cis-site M(2), while the outer doublet is assigned to the trans-site M(1). A random distribution of Fe2+ is observed in fluorine-rich compositions, while slight enrichment of the M(1) site is noticed in hydroxyl compositions, perhaps due to a more sensitive oxidation in situ in M(2) than M(1) sites. The Mössbauer spectrum of siderophyllite K2(Fe 4 2+ Al2)(Si4Al4)O20(OH)4 shows the presence of only one ferrous doublet, which is assigned to M(2) sites. Hence from Mössbauer data we must consider a clintonite (“xanthophyllite”) structure for this mica. The ordered octahedral layer has two distorted ferrous cis-sites and one, more symmetrical, aluminum trans-site.  相似文献   

20.
Simultaneous observations of amplitude scintillations at 40 MHz, 140 MHz and 360 MHz radiated from ATS-6 satellite at 34° E longitude were made at Ootacamund near the magnetic equator in India. It has been found that the frequency variation of scintillation index (S 4) isS 4 ∞f ?n , withn being about 1·2 only for weak scintillations, i.e., so long as the scintillation index does not exceed 0·6 at the lower frequency. For strong scintillations (S 4>0·6) where multiple scattering may be present, the exponentn itself is a function of the intensity of scintillation, the scintillation indices at two frequencies are related by:S 4(f 1)=S 4(f 2) exp [1·3 log(f 2/f 1)(1?S 4(f 2)] so long asf 2/f 1≤3. Thus knowing scintillation index at a given frequency one can estimate the scintillation index at another frequency. This will be of significant importance for communication problems. Evidence is also shown for the reversal of the frequency law in cases of intense scintillations.  相似文献   

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