Direct measurements of latent heat during crystallization and melting of a ugandite and an olivine basalt     

Rebecca A. Lange  Katharine V. Cashman  Alexandra Navrotsky 《Contributions to Mineralogy and Petrology》1994,118(2):169-181

Step-scanning calorimetric measurements using a Setaram HT1500 calorimeter were performed between 800 and 1400°C on two natural samples: a ugandite from the East African rift and an olivine basalt from the western Mexican arc. Our measurements provide the first in-situ quantitative assessment of enthalpy during melting of initially crystalline natural samples. The distribution of latent heat across the liquidus-solidus intervals of the two samples is distinctly different, reflecting significant variation in the sequence and abundance of mineral phases during melting (clinopyroxene and leucite in the ugandite; olivine, clinopyroxene, and plagioclase in the basalt). Our data further indicate that the common assumption of a uniform distribution of latent heat across the liquidus-solidus interval of a magma is a reasonable approximation for the olivine basalt, but is grossly in error for the ugandite. This is due to cotectic precipitation of leucite and clinopyroxene, leading to a large, disproportionate release of latent heat early in the crystallization sequence. The implication for the thermal history of a crystallizing ugandite magma is that therate of heat loss during conductive cooling will unitially be more rapid than the average rate. The net result will be to produce lower magmatic temperatures after a given cooling interval relative to models assuming a uniform release of latent heat. An additional series of scanning calorimetric experiments were performed at variable rates (1,2 and 3°/min) to evaluate the role of kinetics on the distribution of enthalpy during both melting and crystallization of the ugandite and olivine basalt. The results indicate that clinopyroxene is the most important mineral phase in controlling the shapes of the enthalpy profiles during cooling; this is due to its large enthalpy of fusion and its tendency for sluggish nucleation, followed by rapid crystallization at temperatures that vary with cooling rate. The resolution of the calorimeter (in terms of heat detected per unit time) is also important in determining the shapes of theobserved enthalpy profiles during these rapid scans. Estimates based on the observed calorimetric signal associated with melting of olivine, and the lack of a calorimetric signal during melting of leucite, combined with known enthalpies of fusion for the two phases, indicate detection limits of approximately 0.6–1.2 kJ per 5 min increments.  相似文献   

Interaction of cations on octahedral and tetrahedral sites in simple spinels: A comment     

Alexandra Navrotsky 《Physics and Chemistry of Minerals》1984,10(4):192-193

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A thermochemical study of glasses and crystals along the joins silica-calcium aluminate and silica-sodium aluminate     

Alexandra Navrotsky  Gilles Peraudeau  Paul McMillan  Jean-Pierre Coutures 《Geochimica et cosmochimica acta》1982,46(11):2039-2047

Enthalpies of solution in molten 2PbO · B₂O₃ at 985 K are reported for series of glasses xCa_0.5AlO₂-(1?x)SiO₂ (O ≤ x ≤ 0.99) and xNaAlO₂-(1?x)SiO₂ (0 ≤ x ≤ 0.56). The data are compared to values for the corresponding crystalline aluminosilicates and to preliminary data for systems containing KAlO₂ and Mg_0.5AlO₂. The enthalpies of mixing of glasses become more exothermic with increasing basicity of the mono- or divalent oxide. The tendency toward immiscibility on the silica-rich side, indicated by the shape of the heat of mixing curve between x = 0 and x = 0.4, is pronounced in the calcium aluminate system, but not in the sodium aluminate system. The shape of the heat of mixing curve, which is roughly symmetrical about x = 0.5, can be rationalized in terms of glass structure by considering essentially random substitution of Si and Al on a continuous three dimensional tetrahedral framework, with stabilization arising from electrostatic interactions between aluminum and the nonframework cation balancing the destabilizing effects arising from perturbation of the aluminosilicate framework by the nonframework cation. These trends are consistent with the variation of physical properties of aluminosilicate melts.  相似文献   

Subliquidus glass-glass immiscibility along the albite-diopside join     

D.J. Henry  I.D.R. Mackinnon  I. Chan  A. Navrotsky 《Geochimica et cosmochimica acta》1983,47(2):277-282

A calorimetric study has shown that glasses along the albite-diopside join in the system albiteanorthite-diopside have positive enthalpies of mixing. Thermodynamic calculations based on these data describe a nearly symmetric, metastable, subliquidus irascibility gap along the join with a critical temperature at 910 K. The existence of the miscibility gap was tested experimentally by annealing an Ab₅₀Di₅₀ glass at 748 K and 823 K. Annealed glasses were examined by optical microscopy and by scanning and transmission electron microscopy. The glasses showed morphological and chemical features consistent with unmixing of two glass phases. The apparent mechanism of phase separation involves initial spinodal decomposition followed by coarsening to produce 0.1 μm–0.3 μm spherical glass phases.  相似文献   

Thermochemistry and melting properties of basalt   总被引：1，自引：0，他引：1  

M. A. Bouhifd  P. Besson  P. Courtial  C. Gérardin  A. Navrotsky  P. Richet 《Contributions to Mineralogy and Petrology》2007,153(6):689-698

The heat capacities of the liquid, glassy and crystalline phases of an alkali basalt have been determined from relative enthalpies measured between 400 and 1,800 K. Values given by available models of calculation generally agree to within 2% of these results. As derived from the new data and the enthalpy of vitrification measured at 973 K by oxide-melt drop solution calorimetry for the same sample, the enthalpy of fusion of this basalt increases from 15.4 kJ/mol at 1,000 K to 33.6 kJ/mol at 1,800 K. Comparisons between the enthalpies of fusion of basalt and model compositions confirm the small magnitude of the enthalpy of mixing between the molten mineral components of the liquids. Minor variations in the chemical composition have only a small effect in the heat capacity and the enthalpy of melting of basalt. The enthalpies of formation at 298 K from the oxides of the crystallized and glass phases of this alkali basalt are −112.2 and −98.5 kJ/mol, respectively, for a gram formula weight based on one mole of oxide components.  相似文献   

Derivation Of Refractive Index And Temperature Gradients From Optical Scintillometry To Correct Atmospherically Induced Errors For Highly Precise Geodetic Measurements     

Alexandra I. Weiss  Maria Hennes  Mathias W. Rotach 《Surveys in Geophysics》2001,22(5-6):589-596

Refraction effects of optical beams are generally caused by an inhomogeneous propagation medium and are a major source of systematic errors in the precise optical determination of angles and distances in the atmospheric surface layer. In this contribution a method for deriving vertical temperature and refractive index gradients from optical scintillation is presented. Knowledge of these gradients is required for the compensation of atmospherically induced errors for highly precise terrestrial geodetic measurements, like direct transfer and levelling. The advantage of the present optical method is, that temperature and refractive index gradients can be derived as line-averaged values over the propagation path, which is not possible by meteorological point measurements. Field observations have been carried out with a displaced-beam scintillometer over flat terrain and under different atmospheric conditions in order to verify this method. The experiments show, that this method allows to derive accurate correction values for precise terrestrial geodetic measurements.  相似文献   

Sillimanite—disordering enthalpy by calorimetry     

A Navrotsky  R.C Newton  O.J Kleppa 《Geochimica et cosmochimica acta》1973,37(11):2497-2508

Heat of solution measurements in an oxide-melt were performed on samples of natural sillimanite heat-treated in the range 1200–1700°C at pressures of 16–23 kbar. A distinct enthalpy of solution decrement relative to the unheated sillimanite of about 1.3 kc/mole is shown by samples run at 1400–1550°C. Pressure variations in the range 16–23 kbar cause little change in the heat of solution in this temperature range. This pressure-independent ‘plateau’ in heat of solution is interpreted to be due to Al-Si disordering on tetrahedral sites in the sillimanite structure. A simple temperature-dependent disordering model developed by navrotsky and Kleppa (1967) for spinels leads to an Al-Si interchange enthalpy, Δ_Hnt, of16 ± 1 kcal/mole, in good agreement with the value derived by Holdaway(1971) on entirely different grounds.Above 1550°C, larger heat of solution decrements were observed. Microprobe analyses of quenched samples indicate that the sillimanite has not deviated significantly from the ideal formula. Some unknown profound disordering process may account for the heat effects in the very high temperature range.Unit cell volumes of quenched samples also describe a ‘plateau’ region in the temperature range 1400–1550°C. This plateau consists of an increase of the 6 crystallographic axis beginning at 1350°C without much change in the other axes in the range 1350–1550°C. A sudden expansion of the α-axis occurs between 1550 and 1630°C.We conclude that Al-Si disorder of the type postulated by Beger et al. (1970), and Holdaway (1971) has been confirmed calorimetrically for samples heated under pressure in the temperature range 1400–1550°C.  相似文献   

Application of Generalized Likelihood Uncertainty Estimation (GLUE) at different temporal scales to reduce the uncertainty level in modelled river flows     

Ragab Ragab  Alexandra Kaelin  Muhammad Afzal  Ioanna Panagea 《水文科学杂志》2020,65(11):1856-1871

ABSTRACT

In this study, the distributed catchment-scale model, DiCaSM, was applied on five catchments across the UK. Given its importance, river flow was selected to study the uncertainty in streamflow prediction using the Generalized Likelihood Uncertainty Estimation (GLUE) methodology at different timescales (daily, monthly, seasonal and annual). The uncertainty analysis showed that the observed river flows were within the predicted bounds/envelope of 5% and 95% percentiles. These predicted river flow bounds contained most of the observed river flows, as expressed by the high containment ratio, CR. In addition to CR, other uncertainty indices – bandwidth B, relative bandwidth RB, degrees of asymmetry S and T, deviation amplitude D, relative deviation amplitude RD and the R factor – also indicated that the predicted river flows have acceptable uncertainty levels. The results show lower uncertainty in predicted river flows when increasing the timescale from daily to monthly to seasonal, with the lowest uncertainty associated with annual flows.  相似文献   

Discussion of “Thermodynamic parameters of CaMgSi2O6-Mg2Si2O6 pyroxenes based on regular solution and cooperative disordering models” by Holland,Navrotsky, and Newton     

Donald H. Lindsley  Paula M. Davidson  T. J. B. Holland  A. Navrotsky  R. C. Newton 《Contributions to Mineralogy and Petrology》1981,75(3):301-306

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Calculation of effect of cation disorder on silicate spinel phase boundaries     

Alexandra Navrotsky 《Earth and Planetary Science Letters》1977,33(3):437-442

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