离子极化和离子晶体的晶格能——离子极化能的经验计算和非标准型离子晶体的晶格能

In this paper, the discrepancy between lattice energies theoretically calculated and those experimentally determined for the ionic crystals which contain ions having non-inert gas configuration is discussed with the Fajans‘ concept of ionic polarization.Thus, the actual lattice energy U is expressed as the sum of the purely ionic lattice energy Ui calculated from Kapustinskii equation and the polarization energy Up;U=Ui Up An empirical equation is proposed to calculate ionic polarization energy;Up=α Z^*2/r bα c where Z^*z/r is the polarizing power of the cation,a is the polarizability of the anion,ar b and c are the empirical constants which depend on the type of the compounds concerned.Using above expressions,lattice energies of 317 non-standard type erystalline compounds are caleulated and the results well agree with the experimental values and are better than the ealeulations by other authors.     

某些低对称矿物中二价铜离子晶场光谱的计算

Reported in this paper are the expressions for the crystal field potential energy and perturbation matrix elements for the symmetry of C4v, D2h and Ci, by which the crystal field spectra of Cu^2 ions in the minerals such as metatorbernite, conichalcite and turquoise have been calculated. In our calculation, the values uf (r^3) and (r^4)are determined by the empirical radial-wave function cited from reference [1]. The results obtained are essentially consistent with the experimental data.     

Prediction of Liquid Immiscibility in Silicate Melts in Special Reference to Their Free Energies

Currie proposed a cirterion for predicting liquid immiscibility in silicate melts with reference to their free energies efore and after crystal fractionization of a melt.The present authors have calculated the rock analysis data given by Philpotts and proved the validity of Currie‘s method.The authors are particularly interested in the study of immiscibility in the magma in relation with iron deposits.Therefore,they have also calculated the data for artificial silicate melts as well as the data from the famous Kirunavaara iron deposit.     

Lithium Ion Extraction from the High Ration Mg/Li Salt Lake Brine with Ionic Liquid in Triisobutyl Phosphate and Kerosene

正1 Introduction As the lightest metal with the unique properties of energy production and storage,lithium is regarded as the new century energy metal.Lithium and its compounds were widely used in various industrial fields,especially in     

Identification and geochemical significance of polarized macromolecular compounds in lacustrine and marine oils

Polarized macromolecular compounds in typical lacustrine and marine shale oils collected from the Ordos Basin and Tarim Basin of China were analyzed by FT-ICR-MS. Maturity was taken into consideration by diagenesis physical simulation experiments on shale oils, which had been collected at various temperature and pressure stages. The results showed that similar components existed in non-hydrocarbon and asphaltenes and the main peak compound classes of Nl and 02 were potential parameters for identifying typical marine oil and lacustrine oil in China. Nitrogen compounds/（nitrogen compounds and oxygen compounds）, such as Nl/（O2＋Nt）, NL/（Oa＋Nt）, Ni/（NiO1＋N1O2） are the maturity indicators, which are related with C-N and C-O bond energy. Differences in molecular components and weights between marine and lacustrine oils are the effective index to identify source maturity and sedimentary environment.     

旱2井岩石抽提物中未成熟和成熟芳烃系列化合物组成分布的比较

Comparison has been made of the occurence of aromatic series in chloroform fraction between immature and mature sedimentary rocks from the Hang.2 well in Chaidamu Basin. According to the general formula CaH2n-p (p=6, 8, 10, ..., 20), the molecular ion distribution of 11 series have been studied by capillary gas chromatography and GC-MS. It has been found that the immature.mature evolution of aromatic homologous obeys the rules in thermodynamics and can be summaried as: (1) The alkyl side chains decrease and become shorter in compounds of each series. (2) Alkyl and cycloalkanes aromatics (1--3 ring) increase, but cycloalkanes aromatics with more (4-5) rings decrease. (3) Aromatization is observed in alkyl benzene, alkyl naphthalene and alkyl phe.nanthrene series. (4) The bimodal distribution of carbon number curve changes into unimodal distribution. It seems that the variation in aromatic homologous distribution can be used as a potential indicator of maturatlon or as fingerprints for source-rock correlation.     

A Mathematical Calculation Model Using Biomarkers to Quantitatively Determine the Relative Source Proportion of Mixed Oils

It is difficult to identify the source（s） of mixed oils from multiple source rocks, and in particular the relative contribution of each source rock. Artificial mixing experiments using typical crude oils and ratios of different biomarkers show that the relative contribution changes are non-linear when two oils with different concentrations of biomarkers mix with each other. This may result in an incorrect conclusion if ratios of biomarkers and a simple binary linear equation are used to calculate the contribution proportion of each end-member to the mixed oil. The changes of biomarker ratios with the mixing proportion of end-member oils in the trinal mixing model are more complex than in the binary mixing model. When four or more oils mix, the contribution proportion of each end-member oil to the mixed oil cannot be calculated using biomarker ratios and a simple formula. Artificial mixing experiments on typical oils reveal that the absolute concentrations of biomarkers in the mixed oil cause a linear change with mixing proportion of each end-member. Mathematical inferences verify such linear changes. Some of the mathematical calculation methods using the absolute concentrations or ratios of biomarkers to quantitatively determine the proportion of each end-member in the mixed oils are deduced from the results of artificial experiments and by theoretical inference. Ratio of two biomarker compounds changes as a hyperbola with the mixing proportion in the binary mixing model, as a hyperboloid in the trinal mixing model, and as a hypersurface when mixing more than three end- members. The mixing proportion of each end-member can be quantitatively determined with these mathematical models, using the absolute concentrations and the ratios of biomarkers. The mathematical calculation model is more economical, convenient, accurate and reliable than conventional artificial mixing methods.     

气水化合物的水合常数及其在水溶液包裹体多组分挥发分测定中的应用

During the microthermometric measurement(cooling)of aqueous inclusions with multivolatile components,solid crystals of gas clathrates often occur with snow-flower-or soft-ice appearances.The structural formula of these solids is M·nH_2O(where n≥5.67).Many hydrocarbons,related compounds and their binary or multi-component mixtures may generate gas clathrates.This phenomenum is of fundamental importance to the study of inclusions with hydrocarbon aqueous solutions,because this is related to the determination of inclusion parameters and the computation of thermodynamic parameters. In the nature most aqueous inclusions contain not merely one volatile component but multi-volatile components.Therefore,the measurement of aqueous inclusions with multivolatile components is of universal significance and great importance.There have been many studies and available formula or figures about the computation of thermodynamic parameters for aqueous inclusions with one volatile component.Nevertheless,there are few studies concerning with muhivolatile components and it is very difficult to computate thermodynamic parameters for aqueous inclusions with these components. In this paper,hydrated coefficient K is introduced.K_i is the ratio of molar fraction of component i in the gas phase to that in the gas clathrate,or K_i=y_i/x_i.Because K is a function of temperatures and pressures,it can be used to evaluate the temperature-pressure conditions on the phase behavior with muhivolatile components. Based on the regression analysis of available experimental data,the authors have developed computational expression of hydrated coefficients in relation to temperature and pressure for most hydrocarbons and other volatile components,which is helpful to conveniently compute thermodynamic parameters on stability state for elathrates with volatile components.As aqueous inclusions with muhivolatile components are common in the nature,by the use of final melting temperatures of clathrates from mierothermometry and these formula,fluid density of gas phase with valotile components and bulk fluid density of inclusions can be accurately calculated. Furthermore,this method may provide foundations to determine the isochores of inclusions and to calculate trapping temperatures and pressures. Finally,detailed analyses for two computational examples about aqueous inclusions with muhivolatile components are presented.     

Experimental Studies of the Solubility of Cassiterite and the Extraction of Tin from Granitic Melts

Experiments indicate that the solubility of cassiterite can be enhanced by increasing either acidity or alkalinity in hydrothermal solutions as a consequence of the duality of tin.The minimum solubility of cassiterite is found in neutral solutions.F-and CL-coordination compounds of Sn can alternate with hydroxyl coordination compounds with changing pH in the solutions.In this case,F^- and Cl^- and OH^- can be substituted with each other.The dissolution reaction of cassiterite is of reducing nature.High temperature and acidic reducing environment are favorable for the dissolution of cassiterite and the trans-port of Sn^2 compounds in fluids or solutions.High-temperature fluoride and chloride fluids can all dissolve,extract and enrich Sn to form F^- and /or Cl-coordination compounds,However,Fplays a more important role than Cl.F-coordination compounds are more stable and efficient than Cl-coordination compounds during the transport an enrichment of Sn in melts or solutions.The solubili-ty of cassiterite and the amount of Sn extracted from granitic melt depend not only on T,P,pH and Eh in the fluids or solutions,but also on the amounts of dissociated F^- and Cl^- in the fluids.     

Surface and adsorptive properties of wood char particles in soil

Char and soot （black carbon, BC） are highly surface-active materials that can play an important role in contaminant fate and bioavailability in soils and sediments. This report summarizes our research on the influence of adsorbate structure and BC properties on adsorption of organic compounds, and the possible attenuation of BC surface activity by humic substances in the environment. The BC was a maple wood char formed at 400 ℃ in air and under other conditions. The solutes were polar and apolar aromatic compounds. The following points will be discussed. （1） By comparing adsorption to nonporous graphite, it was shown that molecular sieving effects （steric restriction） in the char micropore system occur in the order of increasing substitution on the benzene ring and in the order of increasing fused ring size. （2） By accounting for hydrophobic and steric effects it was shown that aromatic rings substituted with strongly pi-electron-accepting functional groups, such as nitro, undergo pi-pi electron donor-acceptor （EDA） interactions with the pi-donor polyaromatic （graphene） surface of the char. The free energy of adsorption due to pi-pi EDA interactions correlated with the free energy of molecular complexation in chloroform with model compounds representing the graphene surface （napthalene, phenanthrene, pyrene）. （3） A series of chars were prepared of different polarity （O content） but similar surface area and pore size distribution by varying temperature and atmosphere. Single- and bi-solute experiments showed that polar interactions with surface O are not a significant driving force for adsorption of polar compounds. Rather, surface O attracts water molecule clusters that inhibit adsorption of both polar and nonpolar compounds by competition. （4） Aging of char particles in a soil-water suspension strongly reduced char SA and sorption of added benzene. Studies were conducted with dissolved humic （HA） acid, HA-char co-precipitates, Ala＋-HA-char co-flocculates, and soybean oil representing humic lipid components.     

Model of Reflection Spectra of Rock Surface in 2π Space

This paper deals with reflection spectra and polarized reflection spectra of 20 sorts of rock in 2π space, and then creates a model of reflection spectra of rock surface in 2π space. We measured the change of reflection and polarized reflection spectra as altering the incidence angle, vertex angle, azimuth angle, band and polarization. The results show that influence of the incidence angle on spectral curves is very strong. And when the vertex angle is constant, the horizontal azimuth polarizes rock spectra, and distorts the circular spectrum to become elliptic. The polarization influences the reflection intensity of rock spectra, but has no evident influence on the characteristics of wave forms of rock in 2π space. Therefore, we can describe the whole reflection spectral characteristics, including polarization, of rock surface in 2π space by measuring and calculating the e and p values in several key directions.     

PRESSURE GRADIENT FROM THE CONTRIBUTION OF BOTH GEOTHERMAL AND GRAVITY IN THE LITHOSPHERE

1 Introduction The pressure, a scalar quantity, is defined as P = F/S (F is force, S is the area for F) which can be widely used for both solid and fluid. The formula P = g ρh (g-gravitation acceleration,ρ-density, h-depth) is only used for even density static solid and fluid. The delivery of pressure in the fluid follows the law of Pascal, and the average pressure of uneven density fluid can be calculated with the formula of P = g ρh. The temperature influence on pressure is notHU Ba…     

Sorption of nonionic polar pesticides to smectite

Sorption of geosorbents including soils and sediments is a key process controlling the fate and transport of hydrophobic organic compounds （HOCs） in the environment. HOC sorption has been generally correlated to the nature and content of organic matter present in the geosorbents. However, several environments can have organic matter contents low enough so that clay mineral surfaces are the dominant sorbents, including low-organic carbon soils, some ground water aquifers, atmospheric water droplets （e.g. clouds, fogs, and raindrops）, and engineered environmental systems （e.g. clay barriers）. Furthermore, several previous studies demonstrated that clays or clay components in soils sorb HOCs higher than expected, especially those compounds containing strong polar functionalities. Because many environmentally related HOCs including a significant portion of pesticides and herbicides contain polar functional groups, studying the interactions of these compounds with mineral surface at the molecular level is of great theoretical and practical importance. In the present study, we studied sorption of a series of nonionic pesticides （e.g. dichlobenil, carbaryl, alachlor, metolachlor, monuron, diuron, cyanazine） containing polar functional groups and a polycyclic aromatic hydrocarbon, naphthalene, as a control on a reference smectite （SWy-2） saturated with K^＋ using combined batch sorption and FTIR methodologies.     

Experimental Study on the Solubility of Cr^2 in Olivine,Orthopyroxene and Spinel Solid Solutions

Experiments have been performed on the system MgO-SiO2-Cr-O at 0-2.88 GPa and 1100-1450℃,focusing on the stability of Cr^2 in olivine(O1),orthopyroxene(Opx) and spinel(Sp) and its partitioning between these phases.Analytical reagent grade chemicals,MgO,SiO2,Cr2O3.and Cr were used to make starting mixtures.Excess Cr(50%) was then added in these mixtures to ensure that the resultant phases were in equilibrium with the metal Cr.Flux of BaO B2O3(%) was added for facilitating experimental equilibrium and crystal growth.Cr was used as capsule material.All phases in the product were identified by X-ray and analyzed by electron microprobe,The contents of CrO in the different phases(O1,Opx and Sp)were calculated according to stoichiometry.The obtained results of calculation indicate that Cr^3 in Ol and Opx is negligible.The experimental results show;(a) with increasing temperature and decreasing pressure,Cr^2 solubility in Ol,Opx and Sp increases;(b) with in creasing temperature,the partitioning coefficient of Mg and Cr^2 between Ol and Opx decreases,that between Opx and Sp increases,and that between Ol and Sp remains almost unchanged;(c) the effect of pressure on all partitioning coefficients is negligible.     

Biogeochemical Records at Shangsi Section, Northeast Sichuan in China： The Permian Paleoproductivity Proxies

The marine primary producers assimilate the atmospheric CO2 to form the organic carbon in surface water. The organic carbon then settles down through the water column and is removed from the oceans by final preservation in sediments in the form of petroleum or nature gases. The reconstruction of paleoproductlvity will thus improve our understanding of the biological processes in the formation of fossil energy resource and help to locate new sites for future exploration. In this study, biorelated elements P, Cd, Al, Ba, as well as redox sensitive element Mo, were analyzed in the 448 rock samples collected from Permian strata at the Shangsi (上寺) Section, Guangyuan (广元), Northeast Sichuan (四川) in China. On the basis of the Ti content, the nondetrital contents of P, Ca, and Al, denoted as Pxs, Cdxs, and Alxs, were calculated and found to coincide with the TOC content throughout the whole section, with some enrichment intervals being found in the middle part of Chihsia Formation, topmost Maokou (茅口) Formation, and Dalong (大隆) Formation. This suggests that the biorelated elements could be used as proxies for the paleoproductivity here in this section. Baxs, a paleoproductivity indicator widely used in the paleoceanography, shows insignificant correlation with TOC, Pxs, Cdxs, and Alxs, probably arising from the loss of biological barium in anoxic conditions. Compiled with the data of TOC content and Pxs Cdxs, and Alxs, three episodes of enhanced paleoproductivity were identified in Permian strata including the middle part of Chihsla Formation, topmost Maokou Formation, and Dalong Formation.     

Studies on the Thermodynamics and Thermal Chemistry Properties for Lithium Salts and Their Aqueous Solution Systems

正1 Introduction With the industrial development of lithium battery,nuclear and aerospace industry,the demands of metal lithium and its compounds are increasing significantly.Lithium is called as the energy of the metal in the new century(Zhang et al.2001).The total reserve of lithium resources around the world7     

On the Origin of Petroleum Hydrocarbon Gases

The compositional variation of oil-soluble gaseous hydrocarbons in high-pressure in-place oil from more than 40 oil wells in the Northern Jiangsu oil field, China, was studied. Samples in which the effects of the factors of pressure and biodegradation had been got rid of were chosen as the representatives that could really reflect the original composition of hydrocarbon gases. Such samples were compared compositionally with their corresponding hydrocarbons formed by decarboxylation of volatile low-molecular fatty acids. Thus highly correlative regularities were found to exist between them. The numerical values of both are graphically expressed. The two curves on the diagram are very similar. These two sets of values have a simple correlation coefficient of 0.9935, which presents their genetic relation.Based on the study of the formation of gaseous hydrocarbons from decarboxylation of volatile fatty acids, the following regularities of the isomers are revealed:1) n-butyric acid + isobutyric acid = propane:2) 1 2 isopentanoic acid(2-methyl-butyric acid) + n-pentanoic acid = n-butane; and3) 1 2 isopentanoic acid(3-methyl-butyric acid) = isobutane.The thermodynamics of decarboxylation was analysed and the enthalpy change △H, entropy change △S and Gibbs free energy change △G in the following reaction were calculated:CH_3COOH(1)--CH_4(g) + CO_2(g).Thus the author considers that the reaction for the formation of hydrocarbons due to the decarboxylation of fatty acids is an exothermic one with increased entropy and decreased free energy as well as a spontaneous one. According to the CRC rule, the resultant Gibbs free energy change △G is approximately-41.84 kJ/mol, which is well within the range of the energy levels of biophysiological changes.According to the changes in odd-carbon preference in n-alkanes of petroleum and sediments and the analysis of fatty acids and amino acids, it is considered that hydrocarbon gases do not originate from pyrolysis or thermal degradation but from decarboxylation of organisms. But this biological reaction is not ordinary biochemical reaction in the artificial fermentation for generating marsh gas. On the basis of the change tendency of the fatty acid content in the fermentation liquor for marsh gas generation and the change tendency of the carbon isotopes in methane and carbon dioxide in the marsh gas, it can be judged that the biochemical reaction for forming hydrocarbon gases is a special biological one occurring after the fermentation.     

http://www.sciencedirect.com/science/article/pii/S1674987113000510

In this paper,we analyze lithospheric density distribution of China and surrounding regions on the basis of 300300gravity data and 1 1 P-wave velocity data.Firstly,we used the empirical equation between the density and the P-wave velocity difference as the base of the initial model of the Asian lithospheric density.Secondly,we calculated the gravity anomaly,caused by the Moho discontinuity and the sedimentary layer discontinuity,by the Parker formula.Thirdly,the gravity anomaly of the spherical harmonics with 2e40 order for the anomalous body below the lithosphere is calculated based on the model of EGM96.Finally,by using Algebra Reconstruction Techniques(ART),the inversion of 300300residual lithospheric Bouguer gravity anomaly caused by the lithosphere yields a rather detailed structural model.The results show that the lithospheric density distribution of China and surrounding regions has a certain connection with the tectonic structure.The density is relatively high in the Philippine Sea plate,Japan Sea,the Indian plate,the Kazakhstan shield and the Western Siberia plain,whereas the Tibetan Plateau has low-density characteristics.The minimum value of density lies in the north of Philippines,in the Taiwan province and in the Ryukyu island arc.     

A first-principles study of helium diffusion in quartz and coesite under high pressure up to 12GPa

Helium diffusion in mantle minerals is crucial for understanding mantle structure and the dynamic processes of Earth's degassing.In this paper,we report helium incorporation and the mechanism of its diffusion in perfect crystals of quartz and coesite.The diffusion pathways,activation energies(Ea),and frequency factors of helium under ambient and high pressure conditions were calculated using Density Functional Theory(DFT)and the climbing image nudged elastic band(CI-NEB)method.The calculated diffusive coefficients of He in the quartz in different orientations are:D[100]=1.24×10^?6exp.(?26.83 kJ/mol/RT)m²/s D[010]=1.11×10^?6exp.(?31.60 kJ/mol/RT)m²/s.and in the coesite:D[100]=3.00×10^?7exp.(?33.79 kJ/mol/RT)m²/s D[001]=2.21×10^?6exp.(?18.33 kJ/mol/RT)m²/s.The calculated results indicate that diffusivity of helium is anisotropic in both quartz and coesite and that the degree of anisotropy is much more pronounced in coesite.Helium diffusion behavior in coesite under high pressures was investigated.The activation energies increased with pressure:Ea[100]increased from 33.79 kJ/mol to 58.36 kJ/mol,and Ea[001]increased from 18.33 kJ/mol to 48.87 kJ/mol as pressure increased from0 GPa to 12 GPa.Our calculations showed that helium is not be quantitatively retained in silica at typical surface temperatures on Earth,which is consistent with the findings from previous studies.These results have implications for discussion of the Earth's mantle evolution and for recognition thermal histories of ultra-high pressure(UHP)metamorphic terranes.     

Noble Gas Diffusion Mechanism in Lunar Soil Simulant Grains:Results from ~4He~+ Implantation and Extraction Experiments

Experiments on ion implantation were performed in order to better characterize diffusion of noble gases in lunar soil.4He+ at 50 keV with 5×1016 ions/cm2 was implanted into lunar simulants and crystal ilmenite.Helium in the samples was released by stepwise heating experiments.Based on the data,we calculated the helium diffusion coefficient and activation energy.Lunar simulants display similar 4He release patterns in curve shape as lunar soil,but release temperatures are a little lower.This is probably a con...