A universal thermodynamic model of calculating mass action concentrations for structural units or ion couples in aqueous solutions and its applications in binary and ternary aqueous solutions

A universal thermodynamic model of calculating mass action concentrations for structural units or ion couples in ternary and binary strong electrolyte aqueous solution was developed based on the ion and molecule coexistence theory and verified in four kinds of binary aqueous solutions and two kinds of ternary aqueous solutions. The calculated mass action concentrations of structural units or ion couples in four binary aqueous solutions and two ternary solutions at 298.15 K have good agreement with the reported activity data from literatures after shifting the standard state and concentration unit. Therefore, the calculated mass action concentrations of structural units or ion couples from the developed universal thermodynamic model for ternary and binary aqueous solutions can be applied to predict reaction ability of components in ternary and binary strong electrolyte aqueous solutions. It is also proved that the assumptions applied in the developed thermodynamic model are correct and reasonable, i.e., strong electrolyte aqueous solution is composed of cations and anions as simple ions, H2O as simple molecule and other hydrous salt compounds as complex molecules. The calculated mass action concentrations of structural units or ion couples in ternary and binary strong electrolyte aqueous solutions strictly follow the mass action law.

CALCULATING MODEL OF MASS ACTION CONCENTRATIONS FOR Cd-Sb ALLOY MELT

According to the Cd-Sb alloy phase diagram, resistivity, heat capacity, partial molar entropy and viscosity,the structural units of this alloy melt have been determined as Cd and Sb atoms as well as Cd3Sb2, Cd4Sb3 and CdSb compounds.Based on these structural units and the coexistence theory of metallic melt structure involing compound formation,a calculating model of mass action concentrations has been deduced.The calculated mass action concentrations Ncd are in good agreement with measured activities acd. The Gibbs standard free energy of formatioin for above three compunds have been obtained too.

Calculating models of mass action concentrations for NaBr(aq), LiNO_3(aq), HNO_3(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 activities 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 widespread applicability to electrolyte binary aqueous solutions.

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 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.

Calculating model of mass action concentrations for Ag-Au-Cu melts

Based on phase diagrams and measured activities, the calculatingmodel of mass action concentrations for het- erogeneous meltsAg-Au-Cu was formulated. Calculated results agree with the improvedresults of recent research work, Showing that the model formulatedcan reflect the structural characteristics of these melts. In thismodel, without the help Of any empirical parameters, only threeequilibrium constants are used, hence it is simple, lear, andfavorable to the sim- Plification of calculation.

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.

Calculation Models of Mass Action Concentrations for Metallic Melts Involving Monotectic

Based on the phase diagrams, measured activities as well asDeltaG(m) and DeltaG(xs), calculating models of mass action concentrations for metallic melts involving monotectic have been formulated. The calculated results agree with practice on the whole, showing that the models deduced generally can reflect the structural characteristics of these melts. The metastable compounds formed in the melts are of the types A(2)B(3), AB(2), A(2)B(3) or AB and A(2)B(3)+AB etc..

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.

Calculating models of mass action concentrations for structural units or ion couples in RbCl-H_2O binary system and RbCl-RbNO_3-H_2O ternary system

Thermodynamic models of calculating mass action concentrations for structural units or ion couples in RbCl-H2O binary and RbCl-RbNO3-H2O ternary strong electrolyte aqueous solutions were developed based on the ion and molecule coexistence theory at 298.15 K.A transformation coefficient is needed to compare the calculated mass action concentration and the reported activity because they are obtained at different standard states and concentration units.The results show that the transformation coefficients between the calculated mass action concentrations and the reported activities of the same structural units or ion couples in RbCl-H2O binary and RbCl-RbNO3-H2O ternary strong electrolyte aqueous solutions change in a very narrow range.The transformed mass action concentrations of structural units or ion couples in RbCl-H2O binary system are in good agreement with the reported activities. The transformed mass action concentrations of RbCl and RbNO3 in RbCl-RbNO3-H2O ternary solution are also in good agreement with the reported activities,aRbCl and 3RbNOa,with different total ionic strengths as 0.01,0.05,0.1,0.5,1.0,1.5,2.0,3.0 and 3.5 mol/kg,respectively.All those results mean the developed thermodynamic model of strong electrolyte aqueous solutions can reflect structural characteristics of RbCl-H2O binary and RbCl-RbNO3-H2O ternary strong electrolyte aqueous solutions and the mass action concentration also strictly follows the mass action law.

CALCULATING MODELS OF MASS ACTION CONCENTRATIONSFOR MATTES (Cu_2S-FeS-SnS)INVOLVING EUTECTIC

Based on the facts that cations and anions of molten salts and binary basic oxide solid solutions do not separate from each other as well as that the electric conductivities of mattes are greater than that of salts and basic oxide solid solutions, the calculating models of mass action concentrations for binary and ternary mattes involving eutectic have been formulated. The results of calculation agree well with the values measured;this in turn shows that the calculating models can reftect the structural characteristics of the mattes concerned.

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 motallic 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.

Calculating Model of Mass Action Concentrations for Mn-C Melts and Optimization of Thermodynamic Parameters

Based on the phase diagram, the coexistence theory of the metallic melt structure involving compoundformation and the regularity of melts containing saturated phase, a calculating model of mass action concentrationsfor Mn-C melts was formulated. According to the activities (or activity coefficients AM. and γc.), obtained by theUnified Interaction Parameter Model (UIPM), the thermodynamic parameters G and G at higher temperatures (1628～1873 K) were optimized by the repeated try and error method. It is testified that G G(873～1273 K) and G (298～1623 K), obtained at lower temperatures, can also be used at the above-mentionedhigher temperatures. The calculated N. and N agree well with ac. and ac obtained by UIPM. This result showsthat the deduced model can reflect the structural reality of Mn-C 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.

Novel Insight into the Preparation of Ti-6Al-4V Alloy Through Thermite Reduction Based on the Mass Action Concentration

Based on the mass action concentration theory,a novel thermodynamic analysis for the raw material ratio in the procedure of preparing Ti-6Al-4V alloy by aluminothermic reduction process is proposed in this paper,which is originated from TiO_(2),Al particles,and V_(2)O_(5) as feedstocks,and the relevant equilibrium thermodynamics was calculated through this new method.The results show that the range of aluminum addition coefficient in raw material to experiment should be controlled within 61.5%-100%,which can significantly reduce the number of experimental groups.This method is ready to regulate the matter of excessive aluminum content in reactants for materials preparation,especially for those reactions including elements that are effortless to combine with aluminum to form the corresponding intermetallics or alloys.In addition,it can also be used in general metallurgy or material preparation process to effectively predict the composition and proportion of equilibrium components under certain conditions.

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

According to the law of mass action and the coexistence theory of slag structure, the distribution of manganese between MnO FeO SiO 2 and MgO MnO FeO SiO 2 slag melts as well as liquid iron was analyzed. It is shown that K ′ Mn and K MnO are only dependent on temperature and don’t change with basicities and compositions of slag melts. So the distribution of manganese between the above mentioned slag melts and molten iron obeys the law of mass action. But analysis of experimental results from other sources shows that K ′ Mn and K MnO really change with basicities of slag, which is probably arisen from not approaching equilibrium under low basicity slag melts.

Coexistence Theory of Slag Structure and Its Application to Calculation of Oxidizing Capability of Slag Melts

The coexistence theory of slag structure and it's application to calculation of the oxidizing capabilities of slag melts is described. It is shown that the law of mass action can be widely applied to the calculation of oxidizing capabilities of slag melts in combination with the coexistence theory of slag structure.For slag melts containing basic oxides FeO and MnO, their oxidizing capabilities can be expressed by N Fe tO =N FeO +6N Fe 2O 3 , while for slag melts containing basic oxides CaO, MgO, etc., in addition to FeO and MnO, their oxidizing capabilities can be given as N Fe tO =N FeO +6N Fe 2O 3 +8N Fe 3O 4 .

Application of annexation principle to the study of thermodynamic properties of ternary molten salts CaCl_2-MgC_2-NaCl

Based on the practical basis of measured activities and phase diagrams aswell as in the light of the mass action law. the model of inseparable cations and anions of moltensalts and mattes, and the annexation principle of two kinds of solutions in binary melts, thecalculating model of mass action concentrations of molten salts CaCl_2-MgCl_2-NaCl was formulated.The results of calculation not only agree with experimental values, but also obey the mass actionlaw, testifying that the model formulated can embody the structural characteristics of these ternarysalts, and that the model of inseparable cations and anions as well as the annexation principle oftwo kinds of solutions in binary melts are also applicable to these ternary salts.

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.

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 annexationprinciple, calculating models of mass action concentrations for In-Bi-Cu and In-Sb-Cu melts havebeen formulated. Calculated results not only agree well with practical values, but also obey themass action law, showing that the deduced model can reflect the structural reality of given meltasand that the annexation principles is applicable to these tow ternary metallic melts. So long asthere is one from three binary systems constituting the ternary melts, in which the activities ofone component exhibit positive deviation relative to Raoultian behavior, heterogeous meltsinevitably would form, so heterogeneous calculating model should be used to calculate their massaction concentrations. On the contrary, if all the binary melts are homogeneous and their activitiesexhibit negative deviation with respect to the Raoult's law, then the ternary melts formed fromthem will certainly be homogeneous, hence single phase model should be applied.

Thermodynamic properties and mixing thermodynamic parameters of binary homogeneous metallic melts

After the investigation on the thermodynamic properties and mixingthermodynamic parameters of binary homogeneous metallic melts involving compound, peritectic as wellas solid solution, it was found that the equations of mixing free energy DELTA G^m and excess freeenergy DELTA G^(XS) of them can he expressed by the following equations: DELTA G^m = SIGMA x [SIGMAN_i DELTA G_I^(THETA) + RT(SIGMA N_j ln N_j + SIGMA N_i ln N_i )] and DELTA G^(XS) = DELTA G^m -RT(a ln a + b ln b), respectively.