Universal thermodynamic model of calculating the mass action concentrations of components in a ternary strong electrolyte aqueous solution and its application in the NaCl-KCI-H2O system

A universal thermodynamic model of calculating the mass action concentrations of components in a ternary strong elec-trolyte aqueous solution has been developed based on the ion and molecule coexistence theory, and verified in the NaCl-KCl-H2Oternary system at 298.15 K, To compare the difference of the thermodynamic model in binary and ternary strong electrolyte aqueous solutions, the mass action concentrations of components in the NaCI-H20 binary strong electrolyte aqueous solution were also com-puted at 298.15K. A transformation coefficient was required to compare the calculated mass action concentration and reported activ-ity because they were obtained at different standard states and concentration units. The results show that the transformation coeffi-cients between calculated mass action concentrations and reported activities of the same components change in a very narrow range.The calculated mass action concentrations of components in the NaCl-H2O and NaCl-KCl-H2O systems are in good agreement with the reported activities. This indicates that the developed thermodynamic model can reflect the structural characteristics of solutions,and the mass action concentration also strictly follows the mass action law.     

Universal thermodynamic model of calculating the mass action concentrations of omponents in a ternary strong electrolyte aqueous solution and its application in the NaCl-KCl-H_2O system

A universal thermodynamic model of calculating the mass action concentrations of components in a ternary strong elec-trolyte aqueous solution has been developed based on the ion and molecule coexistence theory,and verified in the NaCl-KCl-H2O ternary system at 298.15 K. To compare the difference of the thermodynamic model in binary and ternary strong electrolyte aqueous solutions,the mass action concentrations of components in the NaCl-H2O binary strong electrolyte aqueous solution were also com-puted at 29...     

A thermodynamic model of calculating mass action concentrations for structural units or ion couples in NaClO_4-H_2O and NaF-H_2O binary solutions and NaClO_4-NaF-H_2O ternary solution

A thermodynamic model of calculating mass action concentrations for structural units or ion couples in NaClO4-H2O and NaF-H2O binary solutions and NaClO4-NaF-H2O ternary strong electrolyte aqueous solutions was developed based on the ion and molecule coexistence theory (IMCT). A transformation coefficient was needed to compare the calculated mass action concentration and the reported activity, because they were usually obtained at different standard states and concentration units. The results show that tran...     

Calculating models of mass action concentrations for NaBr（aq）, LiNO3（aq）, HNO3（aq）, and KF（aq） binary solutions

The calculating models of mass action concentrations for electrolyte aqueous solutions NaBr-H2O, LiNO3-H2O, HNO3-H2O, and KF-H2O have been developed at 298.15 K and their molalities ranging from 0.1 mol/kg to saturation according to the ion and molecule coexistence theory as well as mass action law. The calculated mass action concentration is based on pure species as the standard state and the mole fraction as the concentration unit, and the reported activities are usually based on infinite dilution as the standard state and molality as the concentration unit. Hence, the calculated mass action concentration must be transformed to the same standard state and concentration unit. The transformation coefficients between calculated mass action concentrations and reported ac- tivities of the same component fluctuate in a very narrow range. Thus, the transformed mass action concentrations not only agree well with reported activities, but also strictly obey mass action law. The calculated results show that the new developed models can embody the intrinsic structure of investigated four electrolyte aqueous solutions. The results also indicate that mass action law has its wide- spread applicability to electrolyte binary aqueous solutions.     

计算二元电解质水溶液渗透系数的半经验方程及汽液平衡预测

本文提出了一个新的计算二元电解质水溶液渗透系数的半经验方程,该方程为单参数方程,形式简单且计算准确度高。用该方程关联298.15K的二元电解质水溶液的渗透系数,关联精度优于同类型的其他方程。由298.15K的方程参数预测其他温度(273.15～397.8K)下的蒸汽压数据,也得到了满意的结果。     

Thermodynamic analysis of the Ti-Al-N system

Motivated by the application of (Ti, Al)N alloy compound in the coating layer, the ternary phase diagram of Ti-Al-N was analyzed by the calculation of the phase diagram (CALPHAD) technique. The isothermal sections of the Ti-Al-N ternary system were constructed and compared with the literature experimental results. The thermodynamic parameters of the Ti-Al-N ternary sys- tem and the related Ti-N and Al-N binary systems were adopted from literatures, whereas, those of the Ti-Al binary from the literatures were adjusted according to both the ternary and the binary phase equilibria. The consistency between the calculated results and the experimental data shows that considering the ternary thermodynamic relationship, the adjustments to the thermodynamic parameters of the related binaries are necessary.     

二甲胺-三甲胺-水三元系的汽液平衡研究

用泵式沸点仪测定了常压下二甲胺-三甲胺-水三元系在不同液相组成时的沸点，并用间接法TPx推算了二甲胺-水，三甲胺-水的汽相平衡组成y，用最小二乘法求出了此二元体系的液相活度系数模型参数，在二甲胺-水，三甲胺-水两个二元系基础上计算三元系，并回归出二甲胺-三甲胺二元系的Wilson参数，用Wilson模型对所测的数据进行关联，建立该系统汽液平衡的热力学模型并计算平衡时的汽相组成。     

Application of the annexation principle to the thermodynamic property study of ternary metallic melts In—Bi—Cu and In—Sb—Cu

Based on the phase diagrams,measured activities and the annexation principle,calculating models of mass action concentrations for In-Bi-Cu and In-Sb-Cu melts have been formulated.Calculated results not only agree well with practical values,but also obey the mass action law,showing that the deduced model can reflect the structural reality of given melts and that the annexation principle is applicable to these two ternary metallic melts.So long as there is one from three binary systems constituting the ternary melts,in which the activities of one component exhibit positive deviation relative to Raoultian behavior,heterogeous melts inevitably would form,soheterogeneous calculating model should be used to calculate their mass action concentrations.On the contrary,if all the binary melts are homogeneous and their activities exhibit negative deviation with respect to the Raoult‘s law.then the ternary melts formed from them will certainly be homogeneous,hence single phase model should be applied.     

甲醇-丙酸-水多元系汽液平衡研究

用泵式沸点仪测定了在101.325 kPa下甲醇-水、丙酸-水、甲醇-丙酸三个二元系以及甲醇-丙酸-水三元系在不同液相组成时的沸点,并用间接法Tpx推算了甲醇-水、丙酸-水、甲醇-丙酸三个二元系的汽相平衡组成y.三个二元体系活度系数的关联分别用W ilson模型、M argu les模型、Van Laar模型和NRTL模型进行关联,用最小二乘法求出了它们的液相活度系数模型参数.在甲醇-水、丙酸-水、甲醇-丙酸三个二元系基础上计算三元系,用W ilson模型对所测的三元系数据进行关联,建立该系统汽液平衡的热力学模型并计算平衡时的汽相组成y.用面积积分法检验得到很好的热力学一致性.     

Thermodynamic reassessment of Ga-Hg and Mg-Hg systems

The Ga-Hg binary system was thermodynamically assessed by the CALPHAD method, but only configuration contributions were considered to the entropy of the liquid. The Mg-Hg binary system has not been assessed yet. In the assessments of the Ga-Hg and Mg-Hg binary systems, solutions including liquid and hcp (Mg) were treated as substitution solutions, of which the excess Gibbs energies were formulated with the Relich-Kister polynomial. The intermetallic phases in the Mg-Hg binary system, Mg₃Hg, Mg₅Hg₂, Mg₂Hg, Mg₅Hg₃, MgHg, and MgHg₂, were described as stoichiometric compounds. Based on the reported experimental data and thermodynamic properties of the phase diagram, sets of self-consistent parameters describing all phases in the Ga-Hg and the Mg-Hg binary systems were obtained.     

Simulation calculation of solubility of insoluble compound MmAa in complex system

A simulation calculation model for the solubility of insoluble compound M _m A _a in complex system was established. According to coordination equilibrium principle, relevant dissociation reaction, complexation reaction, self-complexation reaction and protonation reaction during insoluble compound dissolving were considered and then the mass balance equations about solubility calculation were obtained. In the case analysis, the solubility of silver chloride in ammonia system was obtained by simulation calculation, and curved surface charts of thermodynamic equilibrium about the total concentration of silver ions, pH and concentration of ammonia ions were drawn correspondingly. The results show that under the conditions of room temperature and 6 mol/L ammonia concentration, the calculated solubility value of silver chloride (34 g/L) is close to the actual value (31 g/L), demonstrating that this model is suitable for solubility calculation of insoluble compound M _m A _a in the complex system.     

铜-水基纳米流体环路热管太阳能热水系统的实验研究

采用"二步法"制备了铜-水基纳米流体,并对纳米流体进行了透射电镜分析。对不同质量浓度下(0.1%、0.15%、0.2%)铜-水基纳米流体的环路热管太阳能热水系统进行了实验研究,分析了环路热管太阳能热水系统中的水箱水温变化、瞬时光热效率,并与去离子水系统进行了对比分析。实验结果表明,纳米铜颗粒的加入增加了液体的导热系数,铜-水基纳米流体更适合作为太阳能重力环路热管热水系统的相变传热工质,且存在一个最佳的纳米流体工质质量浓度(最佳质量浓度为0.15%),可使得环路热管热水系统的传热性能最佳。     

Prediction of water activities in multicomponent solutions of metal chlorides from the thermodynamic properties of corresponding binary systems

Ｉｎｈｙｄｒｏｍｅｔａｌｌｕｒｇｙ ,ｅｌｅｃｔｒｏｌｙｔｅｓｏｌｕｔｉｏｎｉｓｏｆｔｅｎｄｉｓ ｃｕｓｓｅｄ.Ｔｈｅａｃｔｉｖｉｔｙｏｆｗａｔｅｒｉｓｖｅｒｙｉｍｐｏｒｔａｎｔｔｏｓｔｕｄｙｔｈｅｓｏｌｕｔｉｏｎ ,ｗｈｉｃｈｃａｎｂｅｅｍｐｌｏｙｅｄｔｏｃａｌｃｕｌａｔｅｍａｎｙｔｈｅｒｍｏｄｙｎａｍｉｃａｌｐｒｏｐｅｒｔｉｅｓｏｆｉｔ.Ｆｏｒｅｘａｍｐｌｅ ,ｔｈｅａｃｔｉｖｉ ｔｉｅｓｏｆｔｈｅｓｏｌｕｔｅｓｃａｎｂｅｏｂｔａｉｎｅｄｆｒｏｍｉｔｂｙｕｓｉｎｇｃｒｏｓｓ ｄｉｆｆｅｒｅｎｔｉａｔｉ…     

二元非理想溶液过量体积的测定与研究

采用改进的倾斜式稀释膨胀溶液在298.15K 测定液体苯(1)——环已烷(2)的过量体积,并与文献值比较证明倾斜式稀释膨胀计测得数据可靠。又对未见报导的二甲苯(1)——环已烷(2)溶液在299.15K、288.15K 测定不同浓度下的摩尔过量体积数值,并用 Redich—Kister 方程对全浓度范围内的摩尔过量体积进行关联计算,从而为溶液热力学提供有价值的热力学数据。     

Thermodynamic study on reaction path of Hg（ II ） with S（ II ） in solution

The mercury sulfidation experiments were conducted in the pH range from 1 to 13. The results show that Hg(Ⅱ) reacted with equimolar S(Ⅱ) has the lowest remained Hg(Ⅱ) concentration (9.7 μg/L) at pH 1.0 and the highest remained concentration (940.8 ug/L) at pH 13.0. Meanwhile, the changes of pH values were monitored exactly, which reveal that solution pH values change when mixing the same pH value solutions of HgCl_2 and Na_2S. In order to explain the phenomena and determine the reaction paths of Hg(Ⅱ) reacting with S(Ⅱ) in the solution, the concerned thermodynamics was studied. Species of S(Ⅱ)-H_2O system and Hg(Ⅱ)-H_2O system at different pH values were calculated, and then the species distribution diagrams of S(Ⅱ)-H_2O system, Hg(Ⅱ)-H_2O system and Hg(Ⅱ)-Cl~-0H~~-H_2O system were drawn. Combining the experimental data and thermodynamic calculation, the mechanism of Hg(Ⅱ) reacting with S(Ⅱ) was deduced. The results indicate that different species of S(Ⅱ) and Hg(Ⅱ) have the diverse reaction paths to form HgS precipitate at different pH values and the standard Gibbs free energies change(△_rG_m~Θ) of those equations are also calculated, which can provide a guidance for mercury-containing wastewater treatment with Na_2S.     

Thermodynamic calculation on the smelting slag of direct recycling of electric arc furnace stainless steelmaking dust

1　ＩＮＴＲＯＤＵＣＴＩＯＮＥｌｅｃｔｒｉｃａｒｃｆｕｒｎａｃｅ (ＥＡＦ)ｄｕｓｔｈａｓｂｅｅｎｃｌａｓｓｉｆｉｅｄａｓａｈａｚａｒｄｏｕｓｗａｓｔｅｄｕｅｔｏｉｔｓｈｉｇｈｃｏｎｔｅｎｔｏｆｓｏｍｅｈｅａｖｙｍｅｔａｌｓｌｅａｃｈａｂｉｌｉｔｉｅｓｓｕｃｈａｓｚｉｎｃ ,ｌｅａｄ ,ｃａｄｍｉｕｍａｎｄｃｈｒｏｍｉｕｍ ,ｓｏｉｔｈａｓｂｅｅｎｂａｎｎｅｄｆｒｏｍｌａｎｄｆｉｌｌｓｉｎｍａｎｙｃｏｕｎ ｔｒｉｅｓ .Ａｎｅｓｔｉｍａｔｅｄ 1 % 2 %ｍａｓｓｆｒａｃｔｉｏｎｏｆｔｈｅｓｃｒａｐｃｈａｒｇｅｄ…     

Determination of isothermal section of Ni-Re-Hf ternary system at 1 173 K

1　ＩＮＴＲＯＤＵＣＴＩＯＮＴｈｅｎｉｃｋｅｌ ｂａｓｅｄｓｕｐｅｒａｌｌｏｙｓａｒｅｔｈｅｍｏｓｔｗｉｄｅｌｙｕｓｅｄｈｉｇｈ ｔｅｍｐｅｒａｔｕｒｅｓｔｒｕｃｔｕｒａｌｍａｔｅｒｉａｌｓｆｏｒｍａｎｕｆａｃｔｕｒｉｎｇａｅｒｏｎａｕｔｉｃａｌｅｎｇｉｎｅ     

Calculating Model of Mass Action Concentrations for Fe-Cr-P Melts and Optimization of Thermodynamic Parameters

According to the results of research on the thermodynamic propelles of Fe-Cr, Fe-P and Cr-P melts, the measured achvihes of Fe-Cr-P melts from reference sources as well as the coexistence theory of metallic melts structure involving compound formation, a calculating model of the mass action concentrations for Fe-Cr-P melts has been formulated and some of its thermodynamic parameters have been optimized. The calculated mass action concentrations agree with the measured achvities, which shows that this model can reflect the structural reality of Fe-Cr-P melts.     

Structure and Electric Conductivity of Ce-doped Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> Electrolyte Synthesized by Reverse Titration Chemical Coprecipitation

Ce-doped Bi₂O₃ nanopowders were prepared by reverse titration chemical coprecipitation from Bi³⁺ and Ce⁴⁺ containing aqueous solution. Techniques of X-ray diffraction (XRD), transmission electron microscopic (TEM) and Fourier transform infrared spectroscopy (FTIR) were employed to characterize the as-synthesized materials. The XRD patterns indicated that the peaks can be easily indexed to β-Bi₂O₃ and no diffraction peaks of Ce or other impurity phases were detected in the prepared samples. The calculated average crystalline size decreased from 31.72 to 11.96 nm when the Ce content increased from 1 wt% to 10 wt%. The morphology changed from flake-like into the spherical-like with increase in Ce content. The electric conductivity of Ce-doped Bi₂O₃ electrolyte was also investigated by two probe DC method. Conductivity analysis exhibited that the rate of conductivity increased with increasing Ce²⁺ ratio, when the Ce concentration was up to 5 wt%, the as-synthesized Ce-doped Bi₂O₃ electrolyte showed the maximum value of conductivity(0.295 S·cm^–1).     

Calculating Models of Mass Action Concentrations for Ni-Mn and Co-Mn Melts and Optimization of Their Thermodynamic Parameters

According to phase diagrams, measured activities as well as the coexistence theory of metallic melts structure involving compound formation, the calculating models of mass action concentrations for Ni-Mn and Co-Mn melts are formulated and their thermodynamic parameters are optimized. As a result, the calculated mass action concentrations agree well with the corresponding measured activities, showing that these models can reflect the structural characteristics of both Ni-Mn and Co-Mn melts.