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.     

Mg-Al,Sr-Al和Ba-Al熔体的作用浓度计算模型和热力学参数确定

根据相图、质量作用定律和金属熔体结构的共存理论制定了Mg-Al,Sr-Al和Ba-Al熔体的作用浓度计算模型并求得了相关的热力学参数,计算结果符合实际,证明所制定的模型和确定的热力学参数可以反映相应熔体的结构特点,但将相应文献的热力学参数代入同样熔体则未取得符合实际的结果,原因可能与文献中的热力学参数不符合液态下金属熔体内部化学反应的实际有关。     

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

Based on the phase diagrams, reliable reference experimental data and the coexistence theory of metallic melts structure involving compound formation, calculating models of mass action concentrations for Fe-P and Cr-P melts have been formulated. At the same time, some of their thermodynamic parameters have been optimized. The calculated results not only agree well with the measuredvalues, but also obey the mass action law rigorously, this in turn shows that these models can reflect the structural characteristics of corresponding melts.     

Thermodynamic properties and mixing thermodynamic parameters of two-phase metallic melts

Based on the calculating model of metallic melts involving eutectic, the calculating equations of mixing thermodynamic parameters for two phase metallic melts have been formulated in the light of those equations of homogeneous solutions. Irrespective as to whether the activity deviation relative to Raoultian behavior is positive or negative, or the deviation is symmetrical or unsymmetrical, the evaluated results not only agree well with experimental values, but also strictly obey the mass action law. This testifies that these equations can authentically reflect the structural reality and mixing thermodynamic characteristics of two-phase metallic melts. The calculating equations of mixing thermodynamic parameters for the model of two phase metallic melts offer two practical criteria (activity and mixing thermodynamic parameters) and one theoretical criterion (the mass action law).     

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.     

Thermodynamic Properties of Mn-P and Fe-Mn-P Melts

Based on the phase diagrams and the coexistence theory of metallic melts structure involving compound formation, the cal- culating models of mass action concentrations for Mn-P and Fe-Mn-P melts have been formulated. The calculated mass action concen- trations agree well with the corresponding measured activities, this in turn shows that the deduced models can reflect the structural char- acteristics of the melts concerned and there isn't any saturation of phosphorus in both melts.     

Carbon Solubility and Mass Action Concentrations of Fe-Cr-C Melts

An empirical equation of carbon solubility in Fe-Cr-C melts is regressed based on the experimental data from references. Acalculating model of mass action concentrations for these melts is formulated on the basis of the coexistence theory of metaIlic melts in-volving compound formation, the phase diagram of Cr-C system as well as thermodynamic data of Fe-Cr-C melts. According to the mod-el, the standard Gibbs free energies of formation of CrC and Cr3C2 are obtained. Satisfactory agreement between the calculated and me-asured values shows that the model can reflect the structural characteristics of Fe-Cr-C melts.     

Application of annexation principle to the study of thermodynamic properties of Ag-Bi-In metallic melts

Based on the measured activities, the phase diagrams and the annexation principle, the calculating models of mass action concentrations for Ag-Bi and Ag-Bi-In melts have been formulated. The calculated results agree with practice and obey the mass action law, showing that the models formulated can reflect the structural characteristics of both melts. Meanwhile, it confirms that annexation principle is applicable to the Ag-Bi-In metallic melts. The melts involving eulectic which give rise to phase separation, and in which activities exhibit positive deviation from Raoult's law is the basic cause of melts transforming from homogeneous to heterogeneous ones.     

Fe-Si-C熔体的作用浓度计算模型

根据含化合物金属熔体结构的共存理论、相图和Fe－C系亚稳态化合物的有关热力学数据制定了Fe－Si－C熔体的作用浓度计算模型，计算结果符合实际，从而证明所推导的计算模型可以反映本熔体的结构实际．就碳而言，就碳而言，以饱和为标准态的碳作用浓度Nc′可以通过考虑纯物质到饱和标准态的转换系数Lc来求得．     

A Back Look on the Binary Phase Diagrams of Metals from the Mass Action Law and the Coexistence Theory of Metallic Melts

According to the mass action law and the coexistence theory of metallic melts, the mass action concentrations of Cu-Mg, Bi T1 and Ni-Al melts involving compound formation have been calculated. The calculated results show that, except the ultimate case of pure element, when two elements are present in the melts, all structural units (atoms and molecules) without exception will be present in the melts, i.e., their concentrations may change from great to small, but they will not vanish into nothing, and only under such conditions, the calculated results both agree with practice and obey the law of mass action. In view of that over considerable wide composition range, the activities of both elements of the three solid binary alloys mentioned above have been measured, this seems in contradiction with the present relevant phase diagrams, in which the structural units are determined by composition range, so the latter needs further investigation and consideration.     

含共晶体二元金属熔体作用浓度的计算模型

根据混合自由能有最小值，过剩自由能有最大值（或最小值），激冷条件下产生化合物状亚稳相及共晶，分层等现象，针对Ｃｄ－Ｂｉ，Ｇｅ－Ａｌ，Ｂｉ－Ｓｎ，Ｃｄ－Ｓｎ，Ａｇ－Ｃｕ，Ａｌ－Ｇａ；Ｓｉ－Ａｇ，Ｐｂ－Ｓｎ和Ａｌ－Ｓｎ金属熔体推导了作用浓度的计算模型，计算结果与实测值符合较好，从而证明所提出的计算模型符合本类熔体的结构特点。     

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 components in a ternary strong electrolyte aqueous solution and its application in the NaCl-KCl-H2O system

A universal thermodynamic model of calculating the mass action concentrations of components in a ternary strong electrolyte 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 computed at 298.15K. A transformation coefficient was required to compare the calculated mass action concentration and reported activity because they were obtained at different standard states and concentration units. The results show that the transformation coefficients 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...     

Physical Property Model of MnO-SiO_2 System

From the viewpoints of coexistence theory of the slag structure, the investigation on the structural units of MnO-SiO2 system and the chemical reactions between them has been carried out. The relationships between the physical propenies of the slag and the mass action concentrations of its have been set up at certain temperature and slag composition range, which based on the thermodynamic data of the chemtical reactions between the units and the method of linear regression. The calculated data from the model are in good agreement with the measured results. These calculated values are more accurate and systematic than those from other expirical and semi-expirical formulas used at present.     

Mn-Fe-C系活度相互作用参数与温度的关系

实验测定了不同温度下,C在Mn-Fe熔体（x_Mn=0．0407-0．693 0,x_Fe=0．0336-0．7617）中的溶解度。根据Bale和Pehon提出的相互作用参数模型,利用文献报道的Mn-C系的热力学性质,使用测定的和文献报道的Mn-Fe熔体中C的溶解度值,以及文献报道的Mn-Fe-C熔体中Mn的活度系数值、MnO（s）和CO平衡Mn-Fe熔体的组成,通过热力学推导,实验数据处理和线性回归分析,得到Mn-Fe-C系ε_CFe,ε_CFeFe,εCCFe与温度T的关系式。     

Cd──Sb合金熔体作用浓度计算模型

根据Ｃｄ－Ｓｎ合金相图、电阻率、热容量、偏摩尔熵和粘度，确定该合金熔体的结构单元为Ｃｄ原子，Ｓｂ原子以及Ｃｄ３Ｓｂ２，Ｃｄ４Ｓｂ３和ＣｄＳｂ化合物。基于以上结构单元，并依据含化合物金属熔体的共存理论，推导了Ｃｄ－Ｓｂ合金熔体的作用浓度计算模型。理论计算的Ｎｃｄ，与实测的Ｃｄ的活度值ａ（ｃｄ），完全一致。同时也计算出了以上３种化合物的标准自由能。     

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...     

Applicability of mass action law to sulphur distribution between slag melts and liquid iron

According to the mass action law and the coexistence theroy of slag structure,the calculating models of mass action concentration for CaO-MgO-FeO-Fe2O3-SiO2,CaO-MgO-MgO-FeO-Fe2O3-P2O5-SiO2 and CaO-MgO-MnO-FeO-Fe2O3-Al2O3-P2O5-SiO2 slag melts are formulated and sulphur distribution between the slag melts and liquid iron is treated.It is found that Cao,MnO and FeO promote desulphurization,while MgO is detrimental to desulphurization.In addition.the sulphur sidtribution coefficients between the slag melts and liquid are presented.     

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.