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At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
NASA NTRS2006

Partitioning of Ni, Co and V between Spinel-Structured Oxides and Silicate Melts: Importance of Spinel Composition

Partitioning of Ni, Co and V between Cr-rich spinels and basaltic melt has been studied experimentally between 1150 and 1325 C, and at controlled oxygen fugacity from the Co-CoO buffer to slightly above the hematite magnetite buffer. These new results, together with new Ni, Co and V analyses of experimental run products from Leeman [Leeman, W.P., 1974. Experimental determination of the partitioning of divalent cations between olivine and basaltic liquid, Pt. II. PhD thesis, Univ. Oregon, 231 - 337.], show that experimentally determined spinel melt partition coefficients (D) are dependent upon temperature (T), oxygen fugacity (fO2) and spinel composition. In particular, partition coefficients determined on doped systems are higher than those in natural (undoped) systems, perhaps due to changing activity coefficients over the composition range defined by the experimental data. Using our new results and published runs (n =85), we obtain a multilinear regression equation that predicts experimental D(V) values as a function of T, fO2, concentration of V in melt and spinel composition. This equation allows prediction of D(V) spinel/melt values for natural mafic liquids at relevant crystallization conditions. Similarly, D(Ni) and D(Co) values can be inferred from our experiments at redox conditions approaching the QFM buffer, temperatures of 1150 to 1250 C and spinel composition (early Cr-bearing and later Ti-magnetite) appropriate for basic magma differentiation. When coupled with major element modelling of liquid lines of descent, these values (D(Ni) sp/melt=10 and D(Co) sp/melt=5) closely reproduce the compositional variation observed in komatiite, mid-ocean ridge basalt (MORB), ocean island basalt (OIB) and basalt to rhyolite suites.

Righter, K.↗
NASA NTRS2008

How Deep and Hot was Earth's Magma Ocean? Combined Experimental Datasets for the Metal-silicate Partitioning of 11 Siderophile Elements - Ni, Co, Mo, W, P, Mn, V, Cr, Ga, Cu and Pd

Since approximately 1990 high pressure and temperature (PT) experiments on metal-silicate systems have showed that partition coefficients (D) for siderophile (iron-loving) elements are much different than those measured at low PT conditions. The high PT data have been used to argue for a magma ocean during growth of the early Earth. Initial conclusions were based on experiments and calculations for a small number of elements such as Ni and Co. However, for many elements only a limited number of experimental data were available then, and they only hinted at values of metal-silicate D's at high PT conditions. In the ensuing decades there have been hundreds of new experiments carried out and published on a wide range of siderophile elements. At the same time several different models have been advanced to explain the siderophile elements in the earth's mantle: a) intermediate depth magma ocean; 25-30 GPa, b) deep magma ocean; up to 50 GPa, and c) early reduced and later oxidized magma ocean. Some studies have drawn conclusions based on a small subset of siderophile elements, or a set of elements that provides little leverage on the big picture (like slightly siderophile elements), and no single study has attempted to quantitatively explain more than 5 elements at a time. The purpose of this abstract is to update the predictive expressions outlined by Righter et al. (1997) with new experimental data from the last decade, test the predictive ability of these expressions against independent datasets (there are more data now to do this properly), and to apply the resulting expressions to the siderophile element patterns in Earth's upper mantle. The predictive expressions have the form: lnD = alnfO2 + b/T + cP/T + d(1Xs) + e(1Xc) + SigmafiXi + g These expressions are guided by the thermodynamics of simple metal-oxide equilibria that control each element, include terms that mimic the activity coefficients of each element in the metal and silicate, and quantify the effect of variable oxygen fugacity. Preliminary results confirm that D(Ni) and D(Co) converge at pressures near 25-30 GPa and approximately 2200 K, and show that D(Pd) and D(Cu) become too low at the PT conditions of the deepest models. Furthermore, models which force fit V and Cr mantle concentrations by metal-silicate equilibrium overlook the fact that at early Earth mantle fO2, these elements will be more compatible in Mg-perovskite and (Fe,Mg)O than in metal. Thus an intermediate depth magma ocean, at 25-30 GPa, 2200 K, and at IW-2, can explain more mantle siderophile element concentrations than other models.

Righter, Kevin↗
NASA NTRS1970

Solubility of non-polar gases in electrolyte solutions

Solubility theory describes the effects of both concentration and temperature on solute activity coefficients. It predicts the salting-out effect and the decrease in solubility of non-polar gases with increased electrolyte concentration, and can be used to calculate heats of solution, entropies, and partial molal volumes of dissolved gases

Walker, R. L., Jr.↗
NASA NTRS1973

Thermodynamic properties of gases dissolved in electrolyte solutions.

A method based on perturbation theory for mixtures is applied to the prediction of thermodynamic properties of gases dissolved in electrolyte solutions. The theory is compared with experimental data for the dependence of the solute activity coefficient on concentration, temperature, and pressure; calculations are included for partial molal enthalpy and volume of the dissolved gas. The theory is also compared with previous theories for salt effects and found to be superior. The calculations are best for salting-out systems. The qualitative feature of salting-in is predicted by the theory, but quantitative predictions are not satisfactory for such systems; this is attributed to approximations made in evaluating the perturbation terms.

Tiepel, E. W.↗
NASA NTRS1975

Experimental investigation of reaction coronas on olivine in Apollo 14 high-grade breccias

Reaction coronas of pyroxene plus or minus ilmenite occur around clasts of olivine in Apollo 14 high-grade metamorphic breccias. In experiments of several months duration, there was no evidence of corona formation at 1000 C, but at 1050, with oxygen fugacity at or above Ilm-Ru-Fe and below Fe-Fe(1-x)O, incipient coronas formed around Fo(50-70), Fo(68), En(69) + Fe. Reduction of olivine under these conditions is inconsistent with the calculated stability relations and is attributed to uncertainties in the activity coefficient for olivine or pyroxene. The experiments also suggest that vesicularity in the Apollo 14 high-grade breccias may correlate with the amount of glassy material in their unmetamorphosed precursors. The metamorphic event is attributed to burial in a hot ejecta blanket, such as that of the Imbrium event.

Kesson, S. E.↗
NASA NTRS1977

The chemical composition of the cores of the terrestrial planets and the moon

Using models of the quasi-chemical theory of solutions, the activity coefficients of silicon are calculated in the melts Fe-Si, Ni-Si, and Fe-Ni-Si. The calculated free energies of solution of liquid nickel and silicon in liquid iron in the interval 0 to 1400 kbar and 1500 to 4000 K, shows that Fe-Ni-Si alloy is stable under the conditions of the outer core of the earth and the cores of the terrestrial planets. The oxidation-reduction conditions are studied, and the fugacity of oxygen in the mantles of the planets and at the core-mantle boundary are calculated. The mechanism of reduction of silicon is analyzed over a broad interval of p and T. The interaction between the matter of the core and mantle is studied, resulting in the extraction of silicon from the mantle and its solution in the material of the core. It is concluded that silicon can enter into the composition of the outer core of the earth and Venus, but probably does not enter into the composition of the cores of Mercury, Mars, and the moon, if in fact the latter possesses one.

Kuskov, O. L.↗
NASA NTRS1978

Development and evaluation of die and container materials

Commercial high purity ultrafine Si3N4, Al2O3, and SiO2 powders were vacuum dried and stored under nitrogen in sealed containers. Extensive analysis of the chemical, physical, and morphological characteristics of these powders was performed. The interaction of molten silicon with fused quartz was examined in a Knudsen cell using a mass spectrometer. The solubility of oxygen at the melting point of silicon was calculated to be 1.78 times 10 to the 18th power atoms/cu cm, and the activity coefficients of oxygen and silicon monoxide, the major vapor species, were calculated to be 4.83 times 10 to the minus 24th power and 0.0000701, respectively.

Wills, R. R.↗
NASA NTRS1978

Fractionation in the solar nebula. II - Condensation of Th, U, Pu and Cm

Reasonable assumptions concerning activity coefficients allow the calculation of the relative volatility of the actinide elements under conditions expected during the early history of the solar system. Several of the light rare earths have volatilities similar to Pu and Cm and can be used as indicators of the degree of fractionation of these extinct elements. Uranium is considerably more volatile than either Pu or Cm, leading to fractionations of about a factor of 50 and 90 in the Pu/U and Cm/U ratio in the earliest condensates from the solar nebula. Ca,Al-rich inclusions from the Allende meteorite, including the coarse-grained inclusions, have a depletion of U relative to La of about a factor of three, suggesting that these inclusions may have been isolated from the nebular gas before condensation of U was complete. The inclusions, however, can be used to determine solar Pu/U and Cm/U ratios if the rare earth patterns are determined in addition to the other normal measurements.

Boynton, W. V.↗
NASA NTRS1979

Condensation and fractionation of rare earths in the solar nebula

The condensation behavior of the rare earth elements in the solar nebula is calculated on the basis of the most recent thermodynamic data in order to construct a model explaining group II rare earth element patterns in Allende inclusions. Models considered all involve the removal of large fractions of the more refractory heavy rare earth elements in an early condensate, followed by the condensation of the remainder at a lower temperature. It is shown that the model of Boynton (1975) in which one rare earth element component is dissolved nonideally in perovskite according to relative activity coefficients can not reasonably be made to fit the observed group II patterns. A model in which two rare earth components control the patterns and dissolve ideally in perovskite is proposed and shown to be able to account for the 20 patterns by variations of the perovskite removal temperature and the relative proportions of the two components.

Davis, A. M.↗
NASA NTRS1979

Nebular condensation of Ga, Ge and Sb and the chemical classification of iron meteorites

The quantization of the Ga and Ge contents in iron meteorites, which is used as a key parameter in the chemical classification of iron meteorites, is discussed in terms of nebular condensation. The calculation of nebular equilibrium condensation is examined, taking into account the dependence of the activity coefficient on temperature and composition, and recent calculations of the condensation temperatures of Ga, Ge, Sb, Au, As and Cu are presented, noting that Ge is the most volatile siderophile, followed by Ga and Sb. The narrow intragroup ranges of Ga and Ge are interpreted in terms of minimal fractionation during core crystallization, while the larger ranges of Sb are attributed to its significantly smaller solid/liquid distribution coefficient in IIIAB meteorites.

Wai, C. M.↗
NASA NTRS1982

Sulfur-dioxide/water equilibria between 0 and 50 C - An examination of data at low concentrations

In order to resolve the discrepancy noted in values currently used for the first dissociation constant of SO2 in water, the pertinent literature was critically examined and a value of 0.0132 M at 25 C was recommended. An expression correlating this value as a function of temperature for zero-50 C has been developed. Attention is also given to the literature for the Henry's law constant, and a value of 1.242 M/atm at 25 C is recommended. Ionic activity corrections and speciation in more concentrated solutions are discussed, and recommendations are made for estimating the activity coefficients of the various ionic species in solutions of moderate ionic strength.

Maahs, H. G.↗
NASA NTRS1983

Determination of Systems Suitable for Study as Monotectic Binary Metallic Alloy Solidification Models

Succinonitrile-water and diethylene glycol-ethyl salicylate are two transparent systems which have been studied as monotectic binary metallic alloy solidification models. Being transparent, these systems allow for the direct observations of phase transformations and solidification reactions. The objective was to develop a screening technique to find systems of interest and then experimentally measure those systems. The succinonitrile-water system was used to check the procedures. To simulate the phase diagram of the system, two computer programs which determine solid-liquid and liquid-liquid equilibria were obtained. These programs use the UNIFAC method to determine activity coefficients and together with several other programs were used to predict the phase diagram. An experimental apparatus was developed and the succinonitrile-water phase diagram measured. The diagram was compared to both the simulation and literature data. Substantial differences were found in the comparisons which serve to demonstrate the need for this procedure.

Smith, J. E., Jr.↗
NASA NTRS1986

Theoretical and Experimental Flow Cell Studies of a Hydrogen-Bromine Fuel Cell, Part 1

There is increasing interest in hydrogen-bromine fuel cells as both primary and regenerative energy storage systems. One promising design for a hydrogen-bromine fuel cell is a negative half cell having only a gas phase, which is separated by a cationic exchange membrane from a positive half cell having an aqueous electrolyte. The hydrogen gas and the aqueous bromide solution are stored external to the cell. In order to calculate the energy storage capacity and to predict and assess the performance of a single cell, the open circuit potential (OCV) must be estimated for different states of change, under various conditions. Theoretical expressions were derived to estimate the OCV of a hydrogen-bromine fuel cell. In these expressions temperature, hydrogen pressure, and bromine and hydrobromic acid concentrations were taken into consideration. Also included are the effects of the Nafion membrance separator and the various bromide complex species. Activity coefficients were taken into account in one of the expressions. The sensitivity of these parameters on the calculated OCV was studied.

Savinell, R. F.↗
NASA NTRS1988

Partitioning of rare earth elements between hibonite and melt and implications for nebular condensation of the rare earth elements

The effect of oxygen fugacity on the partitioning of REEs between hibonite and silicate melt is investigated in hibonite-growth experiments at 1470 C. The experimental procedures and apparatus are described, and the results are presented in extensive tables and graphs and characterized in detail. The absolute activity coefficients in hibonite are estimated as 330 for La, 1200 for Eu(3+), and 24,000 for Yb. It is inferred that ideal solution behavior cannot be assumed when calculating REE condensation temperatures for (Ca, Al)-rich inclusions in carbonaceous chondrites.

Drake, Michael J.↗
NASA NTRS1991

Reinterpretation of reduction potential measurements done by linear sweep voltammetry in silicate melts

The equilibrium concentrations of Ni between silicate melt and Pt were determined experimentally as a function of oxygen fugacity. The results demonstrate that metallic species derived in linear sweep voltammetry experiments in silicate melts are diffusing into Pt electrodes and not into the melt, as was concluded by previoius studies. This requires reinterpretation of previous linear sweep voltammetry results and recalculation and correction of reported reduction potentials. This paper reports these corrected reduction potentials. Also reported are the activity coefficients for Ni in synthetic basalt and diopsidic melts and for Co in diopsidic melt.

Colson, R. O.↗
NASA NTRS2004

Lunar and Planetary Science XXXV: Terrestrial Planets: Building Blocks and Differentiation

The session "Terrestrial Planets: Building Blocks and Differentiation: included the following topics:Magnesium Isotopes in the Earth, Moon, Mars, and Pallasite Parent Body: High-Precision Analysis of Olivine by Laser-Ablation Multi-Collector ICPMS; Meteoritic Constraints on Collision Rates in the Primordial Asteroid Belt and Its Origin; New Constraints on the Origin of the Highly Siderophile Elements in the Earth's Upper Mantle; Further Lu-Hf and Sm-Nd Isotopic Data on Planetary Materials and Consequences for Planetary Differentiation; A Deep Lunar Magma Ocean Based on Neodymium, Strontium and Hafnium Isotope Mass Balance Partial Resetting on Hf-W System by Giant Impacts; On the Problem of Metal-Silicate Equilibration During Planet Formation: Significance for Hf-W Chronometry ; Solid Metal-Liquid Metal Partitioning of Pt, Re, and Os: The Effect of Carbon; Siderophile Element Abundances in Fe-S-Ni-O Melts Segregated from Partially Molten Ordinary Chondrite Under Dynamic Conditions; Activity Coefficients of Silicon in Iron-Nickel Alloys: Experimental Determination and Relevance for Planetary Differentiation; Reinvestigation of the Ni and Co Metal-Silicate Partitioning; Metal/Silicate Paritioning of P, Ga, and W at High Pressures and Temperatures: Dependence on Silicate Melt Composition; and Closure of the Fe-S-Si Liquid Miscibility Gap at High Pressure and Its Implications for Planetary Core Formation.

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