二元系主要相图类型的热力学推导

本文介绍了混合 Gibbs 自由能-组成曲线的基本原理,并在此基础上,推导了二元低共熔系、分解熔融系、固态无限混溶系、具低共熔点的固态有限混熔系,液态有限混熔系相图以及二元系的旋节线和旋节点。     

三元系相图的主要类型、判读方法及其在岩矿方面的应用

三元系相图在岩石学、矿物学、矿床学以及地球化学等领域中被广泛应用。它不仅是研究岩浆结晶、演化、相变以及矿物共生规律的重要方法之一,而且也是用来探讨壳源、幔源岩浆的重要途径之一。与单元系、二元系相比,其图形复杂,判读亦较难。因篇幅所限,本文仅对三元系相图的主要类型,判读方法以及在岩矿方而的应用,作一概略的介绍。     

杠杆定理在二元相图中的运用法则

二元相图不仅是物理化学的重要内容之一,也是金属学的重要内容之一．它准确地揭示了由二组元组成的物质在平衡状态下的化学成分、温度与组织之间的关系及变化规律．二元相图除了其自身的作用外,主要还借助了杠杆定理这一重要工具．我们目前所用的物理化学、金属学的教材［１］,有关二元相图的论述几乎大同小异：首先将杠杆定理推导一翻,然后举一至两个例子说明一下．至于杠杆定理中的一个支点与两个端点在二元相图中有何含义,由于种种原因,都没有作更深入的探讨．通过多年的教学实践,作者认为,杠杆定理中的两个端点在二元相图中相当…     

辽吉成矿带热液型铅锌矿床矿物组合共生分异的热力学制约——以岫岩红旗铅锌矿床为例

辽吉成矿带上广泛分布着热液型铅锌矿床,对于该类型矿床中矿物共生组合特征和成矿物质迁移沉淀机制的研究是矿床学研究的核心问题之一。通过共生矿物热力学平衡的相关计算,绘制热力学lg[Cu2+]-pH、lg[HS−]-pH和Eh-pH相图,可以有效地诠释成矿流体中成矿元素在迁移、沉淀过程中的物理化学条件。本文以辽吉成矿带上典型的热液型铅锌矿床——岫岩红旗铅锌矿床为例,在对该矿床进行镜下典型矿物共生组合研究的基础上,选取了黄铁矿、黄铜矿、方铅矿和闪锌矿四种矿物进行热力学平衡的相关计算,选取473 K、549 K、648 K三个温度截面绘制了热力学lg[Cu2+]-pH、lg[HS−]-pH和Eh-pH相图,结果显示成矿流体中矿物迁移沉淀机制和矿物共生组合的形成主要受成矿流体的温度、离子活度、pH、Eh多因素制约。此研究对于解释辽吉成矿带上典型热液型铅锌矿床的运移沉淀机制和矿物组合特征具有重要的指导意义。     

《岩石物理化学基础》新书简介

由周珣若、王方正编著的《岩石物理化学基础》试用教材于1983年由武汉地质学院出版。 全书共十二章,正文223页,共约34万字,插图262幅,收集参考文献137篇。1—4章着重介绍岩石物理化学中的基本概念、原理、热力学数据的意义及其计算方法等;第5章氧逸度的估算及其应用,主要涉及成岩过程中氧化还原条件的研究问题;6—10章主要讨论了相律和岩浆岩石学中相图的解释和运用,对一元、二元、三元系各类相图作了详尽的结晶过程     

三元系相图读图浅说(一)

相图是根据物理化学实验数据作出的一种形象地表示实验结果的图件。地质科学中,相图主要应用于结晶学、矿物学、岩石学、矿床学和地球化学等领域的研究中。此外,在冶金、硅酸盐和建材工业上亦应用广泛。本文目的在于帮助读者正确理解和判读三元系相图,通过少数典型图例的剖析而掌握对多数三元系相图的使用,从而为所从事研究的地质学课题服务。本文拟分两期刊载)。     

提高测井曲线自动分层的准确性和精度

目前,用于测井曲线自动分层的数学方法已不少。以数理统计为基础的方差分析、各种最优有序分割等方法能将一组有序序列合理地分割成若干组,但它们难以精确确定层面位置,有时还难以用较清晰的指标来判定最佳分层数目。沃尔什变换,差分函数,活度函数等方法是以曲线形态滤波为基础的方法。其中尤以差分函数、活度函数分析方法更接近于传统的手工解释方法,因而在提高解释的准确性与确定界面位置的精度方面,更便于引用传统经验。本文研究了差分函数与活度函数分析在测井曲线分层中提高分层的推确性与划分界面的精度问题。      

氡气测量在佳木斯城市地下热水普查的应用

在佳木斯城区地下热水调查中,运用了水中氡活度浓度测量和土壤氡活度浓度测量综合方法,有效地克服了城市地热地质调查中的不利因素。通过对水中氡活度浓度及土壤氡活度浓度测量值的正态化变换以及原始氡活度浓度异常分析,明确了氡活度浓度异常对地下热水控制构造的指示作用。通过对氡活度浓度测量值的趋势分析,提取局部异常,综合各种异常信息,确定了城区地下热水的有利远景区。     

钙钛矿-锶钛矿-钠镧钛矿体系化合物晶体化学的研究概况

钙钛矿—锶钛矿—钠镧钛矿三元系是钙钛矿族矿物的典型代表。常温常压下CaTiO3为Pbnm结构，但随温度增高可分别相变为I4／mcm和Pm3m结构；SrTiO3的稳定结构是Pm3m14／mcm相；Na／2Ln1／2TiO3的结构则随Ln代表的元素种类不同而有所差异。三个端员组分在压力下的结构变化均没有明确的结论。在三个二元系中，只有CaTiO3—SrTiO3体系研究较深入，并已给出了T-X相图。本从样品的合成实验及高温和高压原位测量等方面展望钙钛矿型化合物的晶体化学研究及其意义。     

三元系相图读图浅说(二)

(四)具一个不一致熔融二元化合物位于自身初相区外的三元近结系分析及关于反应点的一般规律例如白榴石—钙长石—二氧化硅即属于此种类型(图18)。在相图上首先画出表示温度下降方向的箭头,大多数边界线是析出曲线,白榴石和钾长石之间的边界线是反应曲线,用双箭头表示之。因为钾长石的成分点位于它自身初相区之外,所以钾长石与钙长石之间的边界线不和它们两者成分点的连接线相交。     

Dynamical evolution of multiple stars: Influence of the initial parameters of the system

We have modeled the dynamical evolution of small stellar groups with N=6 components in the framework of the gravitational N-body problem, taking into account possible mergers of stars and ejection of single and binary stars. We study the influence of the initial global parameters of the systems (the mass spectrum, average size, virial factor) on their dynamical evolution. The distribution over states is analyzed for a time equal to 300 initial crossing times of the system. The parameters of binary and stable triple systems that form are studied, as well as the properties of ejected single and binary stars. The rate of dynamical evolution in both expanding and contracting groups is higher than in systems in a state of virial equilibrium. The dynamical evolution is more intense in the case of unequal masses than when the system initially consists of equal-mass stars. In most cases, the evolution of a group ends with the formation of a binary or stable triple system. The semimajor axes of the binaries range from several hundredths to several times the initial size of the system. The distribution of the eccentricities of the binaries formed is consistent with an f(e)=2e law. When the initial size of the group is small, the number of final binaries with large eccentricities, and also of stable triple systems with elongated inner-binary orbits, decreases due to merging. As a rule, stable triple systems are substantially hierarchical (the average ratio of the semimajor axes of the inner and outer binaries is 1: 20). On average, the eccentricities of the inner binaries exceed those of the outer binaries: they are equal to \(\overline {e_{in} } \approx 0.7\) and \(\overline {e_{ex} } \approx 0.5\), respectively. The velocities of ejected stars are from several to several tens of km/s, and tend to increase as the initial size of the system, and hence its virial coefficient, decreases.     

Carbonic inclusions

The paper gives an overview of the phase relations in carbonic fluid inclusions with pure, binary and ternary mixtures of the system CO₂–CH₄–N₂, compositions, which are frequently found in geological materials. Phase transitions involving liquid, gas and solid phases in the temperature range between −192°C and 31°C are discussed and presented in phase diagrams (PT, TX and VX projections). These diagrams can be applied for the interpretation of microthermometry data in order to determine fluid composition and molar volume (or density).     

Physical and dynamical parameters of the multiple system HD 222326

We present the results of our study of the physical and dynamical parameters of the multiple system HD 222326. A new method for determining the individual radial velocities of components in wide binary and multiple systems in the case of small radial-velocity differences (δV _r ≤ the FWHMfor the line profiles) is suggested and tested for both model systems and the binary HD 10009. This testing yielded the component radial velocities V _{r 1,2} for HD 10009, enabling us to derive the center-of mass velocity, V _γ, for the first time. We determined the radial velocities of the components of HD 222326 from high-resolution spectra, and refined the orbital parameters of the subsystems using speckle-interferometric observations. A combined spectroscopic and speckle interferometric analysis enabled us to find the positions of the components in the spectral type—luminosity diagram and to estimate their masses. It is likely that the components are all in various evolutionary stages after leaving the main sequence. We analyzed the dynamical evolution of the system using numerical modeling in the gravitational three-body problem and the known stability criteria for triple systems. The system is probably stable on time scales of at least 10⁶ years. The presence of a fourth component in the system is also suggested.     

三元体系NaVO3-H2NCONH2-H2O 298K相平衡及平衡液相物化性质研究

采用等温平衡溶解平衡法测定了三元体系NaVO3-H2NCONH2-H2O 298K下的溶解度及平衡液相物化性质(密度、电导率、pH值),绘制出了相应的溶解度等温图和物化性质一组成图。此三元体系等温溶解度图属简单共饱型,未产生新的复盐和固溶体。2个结晶区分别对应为盐NaVO3和H2NCONH2,无变量点平衡液相组成为：ω(NaVO3)3．99％,ω(H2NCONH2)40．17％,对应的平衡固相盐为NaVO3和H2NCONH2。     

The prediction of mineral solubilities in natural waters: the NaKMgCaClSO4H2O system from zero to high concentration at 25° C

A chemical model of the seawater system, NaKMgCaClSO₄H₂O, is developed for predicting mineral solubilities in brines from zero to high ionic strengths. The calculated solubilities are shown to be in agreement with the experimental data from gypsum saturation (I < 0.06 m) to bischofite saturation (I > 20 m). The model utilizes activity coefficient expressions recently developed by Pitzer and co-workers and an algorithm for rapidly identifying the coexisting phases and their composition at equilibrium. The activity coefficient expressions are parameterized using binary and ternary system solubility and osmotic data. The results indicate that a free energy model defined by binary and ternary system data will accurately predict solubilities in more complex systems. The algorithm for solving the general chemical equilibrium problem is briefly discussed. The method can be used to model systems with an arbitrary number of possible non-ideal solution phases. The iterative procedure is guaranteed to converge and has been found to be efficient and easy to implement.Calculated phase diagrams associated with the seawater system are compared to experimental data. Our calculations are within experimental accuracy whereas the prediction of other seawater models are in substantial disagreement with the data even at low concentration. The calculation of evaporation sequences is also briefly discussed and qualitatively compared to field data. The mineral assemblages predicted by this method are in substantially better agreement with core samples than the sequences predicted by phase diagram methods (Braitsch, 1971), which do not explicitly include the Ca component.     

三种类型烃-烃不混溶包裹体组合的特征和热力学条件的计算

在自然界广泛分布着烃-烃不混溶体系中捕获的流体包裹体,由于这些包裹体具有复杂的组成和相态,因此不混溶包裹体组合的判别和热力学参数的计算常常难以进行。根据烃-烃不混溶体系中两个端员组分流体包裹体室温下的相态特征和在温度-压力平面图上等容线交点显示的位置,划分成三种类型流体包裹体组合,本介绍了三种类型流体包裹体组合特征,叙述了不混溶烃-烃包裹体组合的测定和判别方法,并且阐述均一化包裹体相态方程和气-液平衡常数原理和方法与此同时列举了自然界简单的三种类型不混溶烃-烃包裹体组合的测定、判别和计算的几个实例,利用相态方程和气-液平衡常数,不但精确地计算出包裹体均一压力,并且精确地计算出流体密度和体积等热力学参数。最后,利用均一成气相和液相的两种包裹体在 p-T 平面图上等容线交点同样计算出流体包裹体组合的捕获温度和压力。     

A local identification technique for geotechnical and geophysical systems

Geotechnical structures and natural soil deposits are massive multi‐phase particulate systems characterized by the development of localized response mechanisms under extreme loading conditions. Identification and analysis of such systems based on inverse boundary value problem formulations and sparse measurements are generally indeterminate. This paper presents an alternative local inverse problem technique. Point‐wise identification analyses of the constitutive behaviour of water‐saturated geotechnical and geophysical systems are performed using acceleration and pore pressure records provided by a cluster of closely spaced sensors. The developed novel technique does not require the availability of boundary condition measurements, or solution of an associated boundary value problem. The constitutive behaviour at a specific location of a soil‐system is analysed independently of adjacent response mechanisms or material properties. Numerical simulations and centrifuge tests of a soil‐retaining wall system are used to demonstrate the capabilities of the developed technique. Copyright © 2003 John Wiley & Sons, Ltd.     

用Hooke-Jeeves方法进行水文地质参数寻优的研究

模型验证阶段的水文地质参数调整一直是地下水数值模拟过程中的关键步骤。传统的参数调试方法如试估—校正法既需要大量的时间，又必须凭借经验进行人工干预。这对于本就缺少经验的人来说是无法逾越的难题。因此前人研究了包括单纯形等多种自动优化方法来反求水文地质参数。本文采用的Hooke-Jeeves法是一种算法简单，便于使用的优化方法，它避免了单纯形法必须先形成一系列单纯形顶点及通过形心寻优的麻烦，而是根据误差下降趋势直接寻优获得结果。方法首先将反求水文地质参数问题简化为一无约束优化问题，最终运用Hooke—Jeeves方法对问题进行求解，是一种简单且实用的方法。