KAlF4及相关氟化物的生成和稳定性

KF-AlF3体系中KAlF4和K3AlF6之间共晶点组成的熔盐作为钎剂大量用于各类铝散热器的钎焊,工业上称为Nocolok方法[1,2].以KAlF4为主体的Nocolok钎剂[1]的合成有多种方法已见诸文献报道[2～4].但迄今为止,文献中尚缺乏KAlF4化合物熔体的各种热力学性质,对其生成、稳定性和熔化性质的研究也未见文献报道.由于KAlF4熔体有不平常的低粘度,低表面张力,在铂器中能自动爬出器壁的类似于"超流体"的特性,加上KAlF4熔体的高腐蚀性,用实验方法测定它的液态性质在技术上存在困难.     

葡萄糖与杂环化合物在甲酰胺中的焓相互作用参数

由于糖具有特殊的生物和生理性质 ,在工业生产中已有广泛应用 ,故其溶液热力学性质已成为人们感兴趣的研究课题之一 .糖在水溶液中的热力学性质已见文献报道 [1] ,但在非水体系中的有关数据则较少报道 .研究表明 ,溶剂介质的变化对溶质的溶剂化状态和溶质间相互作用的影响较大 ,选用酰胺为溶剂可以获得模拟蛋白质环境条件下的溶质 -溶剂、溶质 -溶质间相互作用的信息 [2～ 4] .本文利用微量量热法测得了葡萄糖在杂环化合物与甲酰胺的混合溶剂中的溶解焓 .如果把杂环化合物作为 x,葡萄糖作为 y,按照 Mc Millan- Mayer[5 ] 理论 ,1 mol葡萄…     

乙醇-环己烷体系中NaI活度系数的测定与计算

由于非水溶剂的应用日趋广泛,促使物理化学工作者对于溶剂和溶液性质进行研究,同时开展了有关物理化学数据的测定和积累工作,以利于指导实践[1]。目前文献报道含水混合溶剂中的电解质活度系数较多,但非水混合溶剂中电解质活度系数报道较少。电解质浓溶液活度系数的计算方法目前应用较广的是Pitzer半经验算法[2]。Pitzer的算法中具体物系的β(0)、β(1)等系数需从实测活度系数数据拟合求得。孙仁义等通过测定汽液平衡盐效应的方法研究了盐在混合溶剂中的活度系数[3-4]。最近孙仁义等[5]提出了双液比固定条件下含盐体系汽液平衡数据热力学一…     

Gd-Cu相图的最优化及计算

用实验数据计算二元相图的关键是如何获得所研究系统的热力学函数表达式。如果系统存在精确的热力学数据,那么对这些热力学数据进行优化处理后,有可能通过计算得到准确的相图,这一方面的工作已有详细的报道。然而即使是广泛研究了的系统,从文献中也很难找到可靠的热力学数据。实际上,对很多系统只能得到部分实测相图数据,在     

有化学作用时气体在液体中的溶解度

在一定温度下,难溶性气体在液体中的溶解度与气相中气体的平衡分压之间的关系用亨利定律描述: P_2=k_mm_2 (1)式中“2”表示气体溶质,P_2是与液体呈平衡的气相中溶质的分压,单位为atm,m_2是溶质的溶解度,     

适配体电化学传感器检测汞离子进展

适配体是一小段经体外筛选得到的寡核苷酸序列。适配体中的胸腺嘧啶(T)碱基可与Hg~(2+)形成比双链DNA更加稳定的T-Hg~(2+)-T结构。利用该性质结合电化学测量方法可制作检测Hg~(2+)的特异性强、灵敏度高的适配体电化学传感器,并建立微量Hg~(2+)的检测方法。该文对近年来发展的检测Hg~(2+)的适配体电化学传感器进行了综述和总结,对文献报道的几类传感器的构建过程和检测机理进行了详述,对检测方法的优缺点进行了分析。最后,对此类传感器今后的发展方向提出了展望,引用文献83篇。     

基于团簇结构模型的Na2O-Al2O3-SiO2三元体系熔体吉布斯混合摩尔自由能计算

以三元硅酸盐熔体团簇结构模型为基础,选取了Na₂O-Al₂O₃-SiO₂体系不同成分的团簇结构,采用半经验量子化学方法MNDO/d分别计算该三元体系熔体中不同结构的团簇基元在1473、1873、2000 K温度下的熵、焓、热容和自由能等热力学数据,计算得出不同团簇结构基元的混合自由能,并根据统计热力学波尔兹曼分布定律,推导计算得出Na₂O-Al₂O₃-SiO₂三元体系各成分下的混合摩尔自由能。三元硅酸盐熔体的热力学性质与该熔体的微观结构密切相关。     

煤浆气化过程数学模型的探讨——复杂反应系统平衡组成的计算

本文对煤浆气化过程中复杂反应的化学计量关系及平衡组成计算进行了探讨。建立了电子计算机用数学模型及程序。在已知进料组成和气化条件的情况下,从热力学数据即可计算平衡组成,计算结果与实验值符合较好。     

HgS沉淀平衡体系中Hg~(2+)的测定

正硫化物沉淀法除汞基于S~(2-)与Hg~(2+)形成难溶HgS,通过混凝沉降使HgS与水分离达到除汞的目的,其工艺主要由反应和混凝沉降工段组成;出水剩余总汞包括Hg~(2+)、胶态及悬浮态HgS;出水剩余Hg~(2+)含量可反映反应工段除汞效果,胶态及悬浮态HgS含量可反映混凝沉降工段除汞效果,而总汞可反映工艺总体除汞效果。准确测定HgS沉淀体系中Hg~(2+),可为沉淀反应热力学及动力学研究提供     

化学气相淀积法合成氮化铝薄膜及其工艺设计

对ＡｌＢｒ３－ＮＨ３－Ｎ２体系化学气相淀积法合成Ａ１Ｎ膜进行了热力学分析和工艺设计，研究了在不同淀积温度和体系总压时，体系中主要气态物种的平衡分压和Ａ１Ｎ膜的理论淀积速率与源温和载气流量的关系，并与微波等离子体化学气相淀积Ａ１Ｎ膜的实验结果进行了比较。     

Coordination-cluster model for analyzing interactions in Na-O-H melts

A procedure for calculating the thermodynamic activity coefficients of oxygen and hydrogen in dilute Na-O-H system melts over the temperature range 300–600°C was suggested. The thermodynamic activity coefficients of hydrogen in liquid sodium calculated by the coordination-cluster model equations were used to determine the equilibrium hydrogen pressure over melts. The calculation results were compared with the experimental partial hydrogen pressures over the Na(excess)-Na₂O-NaH system at x _O = x _H. The calculated values were in qualitative agreement with the experimental data.     

Thermodynamic properties of liquid Al-Si and Al-Cu alloys

The partial and integral enthalpies of mixing in liquid Al-Si and Al-Cu alloys were determined by high-temperature isoperibolic calorimetry at 1750±5 and 1590±5, respectively. The thermodynamic properties of Al-Si melts were also studied by electromotive force method in temperature range 950-1270 K. The partial and integral excess Gibbs free energies of mixing in liquid Al-Si and Al-Cu alloys were also calculated from literature data on thermodynamic activity of aluminium. The comparison of our experimental results with literature data has been performed. This revised version was published online in July 2006 with corrections to the Cover Date.     

Stability of smectic phases in the Gay-Berne model

We present a detailed computer simulation study of the phase behavior of the Gay-Berne liquid crystal model with molecular anisotropy parameter kappa=4.4. According to previous investigations: (i) this model exhibits isotropic (I), smectic-A (Sm-A), and smectic-B (Sm-B) phases at low pressures, with an additional nematic (N) phase between the I and Sm-A phases at sufficiently high pressures; (ii) the range of stability of the Sm-A phase turns out to be essentially constant when varying the pressure, whereas other investigations seem to suggest a pressure-dependent Sm-A range; and (iii) the range of stability of the Sm-B phase remains unknown, as its stability with respect to the crystal phase has not been previously considered. The results reported here do show that the Sm-A phase is stable over a limited pressure range, and so it does not extend to arbitrarily low or high pressures. This is in keeping with previous investigations of the effect of molecular elongation on the phase behavior of Gay-Berne models. A detailed study of the melting transition at various pressures shows that the low-temperature crystalline phase melts into an isotropic liquid at very low pressures, and into a nematic liquid at very high pressures. At intermediate pressures, the crystal melts into a Sm-A liquid and no intermediate Sm-B phase is observed. On the basis of this and previous investigations, the reported Sm-B phase for Gay-Berne models appears to be a molecular solid rather than a smectic liquid phase.     

Phase equilibria in the CsUO system in the temperature range from 873 to 1273 K

Portions of the cesium-uranium-oxygen system have been investigated between 873 and 1273 K and a phase diagram has been constructed using our data and the data of other workers in the field. A consistent set of measured and estimated thermodynamic data for cesium uranates has been used to calculate the equilibrium cesium partial pressure and the equilibrium oxygen partial pressure over two and three phase regions in the CsUO system. For a given temperature, the equilibrium cesium partial pressure in a two phase region decreases as the equilibrium oxygen partial pressure increases.     

Partial pressures of Te2 and thermodynamic properties of Ga–Te system

The partial pressures of Te₂ in equilibrium with Ga_1−xTe_x samples were measured by optical absorption technique from 723 to 1373 K for compositions, x, between 0.333 and 0.612. To establish the relationship between the partial pressure of Te₂ and the measured optical absorbance, the calibration runs of a pure Te sample were also conducted to determine the Beer’s law constants. The partial pressures of Te₂ in equilibrium with the GaTe(s) and Ga₂Te₃(s) compounds, or the so-called three-phase curves, were established. From the partial pressures of Te₂ over the Ga–Te melts, partial molar enthalpy and entropy of mixing for Te were derived and they agree reasonably well with the published data. The activities of Te in the Ga–Te melts were also derived from the measured partial pressures of Te₂. These data agree well with most of the previous results except those determined by Predel et al. [Z. Metallkde. 66 (1975) 268]. The possible reason for the high activity of Te measured by Predel et al. [Z. Metallkde. 66 (1975) 268] for x<0.60 is discussed.     

The thermodynamic properties of Al-Si system melts

The thermochemical properties of Al-Si system melts were determined by an improved isoperibolic calorimetry method. The data obtained correlated with the reliable partial and integral enthalpies of mixing reported in the literature. The method developed was used to model the thermodynamic properties of melts with the use of the liquidus coordinates of the phase diagram of the Al-Si system. The modeled and experimental results were in close agreement with each other.     

Liquid-vapor equilibrium of dilute aqueous solutions of ethanol and 2-propanol

An automated vapor pressure apparatus has been used to obtain highly precise values of the total pressure and composition of aqueous solutions of ethanol and of 2-propanol in the water-rich region at 25 and 35°C. From these results, values of the partial pressures and fugacities of the components and osmotic coefficients have been inferred. Interaction virial coefficients derived from the present results are compared with interaction parameters previously reported for alcohol molecules in dilute aqueous solution. A discussion is given of the relative importance of hydrophobic effects and hydrogen-bonding in producing the unusual thermodynamic properties of aqueous alcohol solutions.     

Vapor pressure and activity of components of melts formed by manganese chloride and chlorides of alkaline-earth metals

The boiling points of melts were measured at different pressures over the melts for certain concentrations of components of the liquid phase in binary systems constituted by manganese chloride and chlorides of alkaline-earth metals. The temperature dependences of the saturated vapor pressure, normal boiling points, and enthalpies of evaporation were calculated. The concentration dependences of the thermodynamic activities of the components of four binary systems were analyzed.