Concentrated electrolyte solutions at high temperatures and pressures

A survey is given of recent experimental results obtained from high-temperature, high-pressure investigations with water, aqueous solutions, and ionic fluids. Data on the static dielectric constant of water to 550°C and 5 kbar are given and discussed with respect to their relation to water structure. Infrared and Raman spectra of HDO in pure water have been obtained to 400°C and 4 kbar, which give information on hydrogen bonding. Xe–H₂O and CO₂–H₂O mixtures were investigated in the infrared. Ni(II) and Cu(II) complexes were investigated by absorption spectroscopy in aqueous solutions of high chloride content to 350°C and 2–6 kbar. The gas-liquid critical point of ammonium chloride was found at 880°C and 1635 bars. This fluid appears to be predominantly ionic even in the critical region. The possibility of converting pure polar fluids such as ammonia and water into concentrated ionic solutions by self-ionization at very high pressures is mentioned.This paper was presented at the symposium, The Physical Chemistry of Aqueous Systems, held at the University of Pittsburgh, Pittsburgh, Pennsylvania, June 12–14, 1972, in honor of the 70th birthday of Professor H. S. Frank.     

Erosion of efficiency in non-uniform linear chromatography

In linear chromatography (i.e. chromatography performed in the absence of sample overloading), when the plate height of a column is roughly uniform along its length, variations in the velocities of solutes are the only possible causes of erosion of efficiency. The sources of these variations (variations in capacity ratio and in the density of the mobile phase, etc.) play no direct role in the erosion of efficiency except through their effect on solute velocities. In other words, what eventually causes the erosion of efficiency is merely variation in the time required for solutes to traverse equally small segments of a column. Significant erosion can only arise from abrupt and deep deceleration of solutes in one or several relatively small segments of a column. If erosion of efficiency caused by pressure gradients in linear SFC is to be large, the depth and the sharpness of the deceleration of a solute must go beyond that hitherto confirmed experimentally. Many relevant examples are analyzed graphically.     

High-pressure phase transition in LiBH4

The high-pressure phase transition from ambient pressure α-LiBH₄ to high-pressure β-LiBH₄ was observed by Raman spectroscopy and X-ray diffraction between 0.8 and 1.1 GPa. The phase boundary between these two phases was mapped over a large range of temperatures using thermal conductivity studies and differential thermal analysis. The structure of the high-pressure phase could not be identified due to small number of experimentally observed reflections, but it was shown that it is different from previously reported theoretical predictions.     

High-pressure structural trends of Group 15 elements: simple packed structures versus complex host-guest arrangements

The Group 15 elements P, As, Sb, and Bi all have layered structures consisting of six-membered rings under ambient conditions and attain the body-centered cubic (bcc) structure at the highest pressures applied. In the intermediate pressure region, however, phosphorus and its heavier congeners behave profoundly differently. In this region P first attains the open packed simple cubic (sc) structure for a wide range of pressures and then transforms into the rarely observed simple hexagonal (sh) structure. For the heavier congeners complex, incommensurately modulated host-guest structures emerge as intermediate pressure structures. We investigated the high-pressure behavior of P and As by ab initio density functional calculations in which pseudopotentials and a plane wave basis set were employed. The incommensurately modulated high-pressure structure of As was approximated by a supercell. Our calculations reproduced the experimentally established pressure stability ranges of the sc and sh structures for P and the host-guest structure for As very well. We found that the sc and especially the sh structure are decisively stabilized by the admixture of d states in the occupied levels of the electronic structure. This admixture releases s-s antibonding states above the Fermi level (s-d mixing). With pressure, s-d mixing increases rapidly for P, whereas it remains at a low level for As. As a consequence, the band energy contribution to the total energy determines the structural stability for P in the intermediate pressure region, giving rise to simple packed structures. On the other hand, in the intermediate pressure region of the heavier Group 15 elements, a delicate interplay between the electrostatic Madelung energy and the band energy leads to the formation of complex structures.     

Structural evolution of (Ca0.35Sr0.65)TiO3 perovskite at high pressures

Lattice parameters of a synthetic powder sample of Ca_0.35Sr_0.65TiO₃ perovskite have been determined by the method of Le Bail refinement, using synchrotron X-ray diffraction patterns collected at pressures up to 15.5 GPa with a membrane-driven diamond anvil cell. At ambient conditions, diffraction data were consistent with the I4/mcm structure reported previously in the literature for the same composition. Diffraction data collected at high pressures were consistent with tetragonal (or, at least, pseudo-tetragonal) lattice geometry, and no evidence was found for the development of any of the orthorhombic structures identified in other studies of (Ca, Sr)TiO₃ perovskites. Additional weak reflections, which could not be accounted for by the normal I4/mcm perovskite structure, were detected in diffraction patterns collected at pressures of 0.9-2.5 GPa, and above ∼13.5 GPa, however. Small anomalies in the evolution of unit cell volume and tetragonal strain were observed near 3 GPa, coinciding approximately with breaks in slope with increasing pressure of bulk and shear moduli for a sample with the same composition which had previously been reported. The anomalies could be due either to new tetragonal↔tetragonal/pseudo-tetragonal phase transitions or to subtle changes in compression mechanism of the tetragonal perovskite structure.     

Free energies of transfer of complexes of the type MCl2py4 between pyridine and other solvent media

Solubility isotherms are reported for the NiCl₂·4py, MnCl₂·4py, and MnCl₂·2py solid pyridinates in a number of pyridine+diluent mixtures at 25°C. Activity coefficients of the solvent components have been derived from the total vapor pressures measured by a static method. The standard free energies of transfer for the NiCl₂py₄ and MnCl₂py₄ complexes are the same, within the experimental error, in the pyridine+aprotic diluent mixtures, while marked differences are observed in the pyridine+chloroform mixtures. Marked deviations are observed for chloroform and 1,2-dichloroethane from a correlation between the standard free energy of transfer of the complexes, on one hand, and the Hildebrand's solubility parameter of the solvent, on the other, the latter correlation being roughly valid for aprotic solvents. The deviations are tentatively ascribed to hydrogen bond formation of the type H... between the protic solvents and the coordinated pyridine molecules, enhanced by the d electron delocalization.     

煤中有机硫形态结构和热解过程硫变迁特性的研究

利用热解 质谱并结合固定床热解反应装置，对煤中有机硫的形态主其对加氢热解过程 变迁特性的影响，进行了较系统的研究。结果表明，煤中有机硫的形态结构在褐煤中主要以脂肪族、芳香族硫化物为主，而在 煤中则主要以各种不同芳构化程度的噻吩结构为主，初步表明煤中有机硫形态结构随煤变质程度的变迁呈较强的连续递变性。煤热解过程中硫在呼产物中的变迁和分布与煤中有机硫的形态结构特点密切相关。较高芳构化噻吩结构不完全的氧     

考虑水-力耦合和不同应力路径的砂岩卸荷力学特性试验

为研究不同渗透压力条件下的岩石卸荷力学特性,选取砂岩为研究对象,开展了不同渗透压力和不同应力路径下的三轴卸荷试验,并与常规三轴试验进行对比,比较了不同应力路径下的岩石强度特性,分析了渗透压力对岩石变形和强度参数的影响。试验结果表明：渗透压力的增大会弱化岩石强度,岩石的峰值强度随渗透压力的增大而降低,而轴向变形随渗透压力增大而增加,渗透压力越大,岩石的压密段特征越明显;针对两种不同的卸荷应力路径,恒轴压卸围压路径条件下,岩石的黏聚力不断降低,内摩擦角不断增加,而加轴压卸围压路径条件下,岩石的黏聚力不断增加,内摩擦角逐渐降低。     

高层建筑外附雨篷的表面风压和气动力系数

采用风洞试验方法研究高层建筑外附雨篷的风压特征,分析风压系数、风压相关性、非高斯性和整体升力系数随风向角的变化,给出围护结构的设计风压,最后研究倾角和出挑长度对整体力系数的影响. 研究发现,高层建筑外附雨篷上表面风压系数在正迎风时最大值接近1.4,系气流受到后方高层建筑的阻挡下翻导致;上、下表面的最大整体压力系数出现正迎风情况,最大值分别为1.24和0.76;上、下表面的最大整体升力系数出现侧风面,最大值分别为1.13和1.01;上下叠加后测点风压的非高斯性比单表面增强;上表面和下表面的升力系数在0°~70°风向呈现高斯分布,在80°~180°风向呈现较强的非高斯分布;高层建筑外附雨篷上表面的极值正压大于下表面;雨篷整体升力系数按照倾角-10°、0°、10°依次递增.     

超高压高CO2气藏偏差系数图版扩展与应用

Standing-Katz图版法确定天然气偏差系数是目前最常用、最基础的方法之一,但存在人工读值误差大、在超高压（拟对比压力大于15）和高CO₂含量天然气使用受限等问题。设计单组分偏差系数测定实验,结合Standing-Katz图版曲线变化规律,将图版拟对比压力扩展到30,拟对比温度扩展到3.6,并将图版数字化;基于不同CO₂含量偏差系数测定实验结果,推导了考虑不同CO₂含量的天然气拟临界压力、拟临界温度计算新模型,与常规非烃校正模型相比,新模型计算精度更高,适用范围更广。进一步将新临界参数校正模型嵌入到偏差系数扩展图版中,得到不同CO₂含量的偏差系数扩展图版,该图版在南海西部超高温高压、高CO₂含量天然气偏差系数计算中误差较小（不超过3%）,应用效果良好。