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...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.展开更多
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 saturati...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.展开更多
According to the mass action law and the coexistence theory of slagstructure, the calculating models of mass action concentration for CaO-MgO-FeO-Fe_2O_3-SiO_2,CaO-MgO-MnO-FeO-Fe_2O_3-P_2O_5-SiO_2 and CaO-MgO-MnO-FeO-...According to the mass action law and the coexistence theory of slagstructure, the calculating models of mass action concentration for CaO-MgO-FeO-Fe_2O_3-SiO_2,CaO-MgO-MnO-FeO-Fe_2O_3-P_2O_5-SiO_2 and CaO-MgO-MnO-FeO-Fe_2O_3-Al_2O_3-P_2O_5-SiO_2 slag melts areformulated and sulphur distribution between the slag melts and liquid iron is treated. It is foundthat CaO, MnO and FeO promote desulphurization, while MgO is detrimental to desulphurization. Inaddition, the sulphur distribution coefficients between the slag melts and liquid iron andpresented.展开更多
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 ho...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 unsym-metrical, 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).展开更多
Based on the atomicity and molecularity as well as the consistency ofthermodynamic properties and activities of metallic melts with their structures, the coexistencetheory of metallic melts structure involving compoun...Based on the atomicity and molecularity as well as the consistency ofthermodynamic properties and activities of metallic melts with their structures, the coexistencetheory of metallic melts structure involving compound has been suggested. According to this theory,the calculating models of mass action concentrations for different binary metallic melts have beenformulated. The calculated mass action concentrations agree well with corresponding measuredactivities, which confirms that the suggested theory can reflect the structural characteristics ofmetallic melts involving compound and that the mass action law is widely applicable to this kind ofmetallic melts.展开更多
Based on the coexistence theory of metallic melts involving compound formation, the theoretical calculation equations of mixing thermodynamic parameters are established by giving up some empirical parameters in the as...Based on the coexistence theory of metallic melts involving compound formation, the theoretical calculation equations of mixing thermodynamic parameters are established by giving up some empirical parameters in the associated solution model. For Fe-Al, Mn-Al and Ni-Al, the calculated results agree well with the experimental values, testifying that these equations can exactly embody mixing thermodynamic characteristics of these melts.展开更多
Based on the phase diagrams and the mass action law in combination with the coexistence theory of metallic melts structure, the calculation model of mass action concentration for Mg-Al, Sr-Al and Ba-Al was built, and ...Based on the phase diagrams and the mass action law in combination with the coexistence theory of metallic melts structure, the calculation model of mass action concentration for Mg-Al, Sr-Al and Ba-Al was built, and their thermodynamic parameters were determined. The agreement between calculated and measured results shows that the model and the determined thermodynamic parameters can reflect the structural characteristics of relevant melts. However, the fact that the thermodynamic parameters from literature don ′t give the value agree with the measured result may be due to unconformity of these parameters to real chemical reactions in metallic melts.展开更多
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 w...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.展开更多
The law of mass action, based on maxwellian statistics, cannot explain recent epicatalysis experiments but does when generalized to non-maxwellian statistics. Challenges to the second law are traced to statistical het...The law of mass action, based on maxwellian statistics, cannot explain recent epicatalysis experiments but does when generalized to non-maxwellian statistics. Challenges to the second law are traced to statistical heterogeneity that falls outside assumptions of homogeneity and indistinguishability made by Boltzmann, Gibbs, Tolman and Von Neumann in their H-Theorems. Epicatalysis operates outside these assumptions. Hence, H-Theorems do not apply to it and the second law is bypassed, not broken. There is no contradiction with correctly understood established physics. Other phenomena also based on heterogeneous statistics include non-maxwellian adsorption, the field-induced thermoelectric effect and the reciprocal Hall effect. Elementary particles have well known distributions such as Fermi-Dirac and Bose Einstein, but composite particles such as those involved in chemical reactions, have complex intractable statistics not necessarily maxwellian and best determined by quantum modeling methods. A step by step solution for finding the quantum thermodynamic properties of a quantum composite gas, that avoids the computational requirement of modeling a large number of composite particles includes 1) quantum molecular modeling of a few particles, 2) determining their available microstates, 3) producing their partition function, 4) generating their statistics, and 5) producing the epicatalytic parameter for the generalized law of mass action.展开更多
Application of equations of mixing thermodynamic parameters formulated on the basis of the coexistence theory of metallic melts in Ba-Al, Mg-Al, Sr-Al and Cu-Al melts leads to fruitful results that not only the evalua...Application of equations of mixing thermodynamic parameters formulated on the basis of the coexistence theory of metallic melts in Ba-Al, Mg-Al, Sr-Al and Cu-Al melts leads to fruitful results that not only the evaluated mass action concentrations agree well with the measured activities, but also the calculated mixing thermodynamic parameters are quite coincident with the experimental values. Moreover, the calculated mass action concentrations strictly obey the mass action law. The evaluated mixing thermodynamic parameters have very fine regularity: the mixing free energy is composed of standard free formation energies of all compounds and chemical potentials of all structural units at equilibrium; the mixing enthalpy consists of standard formation enthalpies of all compounds; the mixing entropy is composed of standard entropies of all compounds and configuration entropies of all structural units at equilibrium. As the equations of mixing thermodynamic parameters formulated are widely applicable to metallic melts involving compound formation, they can be used as the second practical criterion to determine whether thermodynamic models of metallic melts are correctly formulated.展开更多
According to the mass action law and the coexistence theory of metallic melts, the mass action concentrations of Cu-Mg, Bi-Tl and Ni-Al melts involving compound formation have been calculated. The calculated results s...According to the mass action law and the coexistence theory of metallic melts, the mass action concentrations of Cu-Mg, Bi-Tl 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.展开更多
A new curve fitting method with its mathematical models derived from the mass action law is presented which is applicable to several in vitro radioassays including RIA and RBA. Experiments revealed that the robustness...A new curve fitting method with its mathematical models derived from the mass action law is presented which is applicable to several in vitro radioassays including RIA and RBA. Experiments revealed that the robustness of this method is better than the conventional methods like Woolf plot in RBA and 4- parameter logistic plot in RIA. However, the robustness of this method is only relative: in some cases of RIA and RBA, the bias of the results may still be too large to be acceptable. Further improvement is expected to be studied.展开更多
文摘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.
文摘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.
文摘According to the mass action law and the coexistence theory of slagstructure, the calculating models of mass action concentration for CaO-MgO-FeO-Fe_2O_3-SiO_2,CaO-MgO-MnO-FeO-Fe_2O_3-P_2O_5-SiO_2 and CaO-MgO-MnO-FeO-Fe_2O_3-Al_2O_3-P_2O_5-SiO_2 slag melts areformulated and sulphur distribution between the slag melts and liquid iron is treated. It is foundthat CaO, MnO and FeO promote desulphurization, while MgO is detrimental to desulphurization. Inaddition, the sulphur distribution coefficients between the slag melts and liquid iron andpresented.
文摘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 unsym-metrical, 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).
文摘Based on the atomicity and molecularity as well as the consistency ofthermodynamic properties and activities of metallic melts with their structures, the coexistencetheory of metallic melts structure involving compound has been suggested. According to this theory,the calculating models of mass action concentrations for different binary metallic melts have beenformulated. The calculated mass action concentrations agree well with corresponding measuredactivities, which confirms that the suggested theory can reflect the structural characteristics ofmetallic melts involving compound and that the mass action law is widely applicable to this kind ofmetallic melts.
文摘Based on the coexistence theory of metallic melts involving compound formation, the theoretical calculation equations of mixing thermodynamic parameters are established by giving up some empirical parameters in the associated solution model. For Fe-Al, Mn-Al and Ni-Al, the calculated results agree well with the experimental values, testifying that these equations can exactly embody mixing thermodynamic characteristics of these melts.
文摘Based on the phase diagrams and the mass action law in combination with the coexistence theory of metallic melts structure, the calculation model of mass action concentration for Mg-Al, Sr-Al and Ba-Al was built, and their thermodynamic parameters were determined. The agreement between calculated and measured results shows that the model and the determined thermodynamic parameters can reflect the structural characteristics of relevant melts. However, the fact that the thermodynamic parameters from literature don ′t give the value agree with the measured result may be due to unconformity of these parameters to real chemical reactions in metallic melts.
文摘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.
文摘The law of mass action, based on maxwellian statistics, cannot explain recent epicatalysis experiments but does when generalized to non-maxwellian statistics. Challenges to the second law are traced to statistical heterogeneity that falls outside assumptions of homogeneity and indistinguishability made by Boltzmann, Gibbs, Tolman and Von Neumann in their H-Theorems. Epicatalysis operates outside these assumptions. Hence, H-Theorems do not apply to it and the second law is bypassed, not broken. There is no contradiction with correctly understood established physics. Other phenomena also based on heterogeneous statistics include non-maxwellian adsorption, the field-induced thermoelectric effect and the reciprocal Hall effect. Elementary particles have well known distributions such as Fermi-Dirac and Bose Einstein, but composite particles such as those involved in chemical reactions, have complex intractable statistics not necessarily maxwellian and best determined by quantum modeling methods. A step by step solution for finding the quantum thermodynamic properties of a quantum composite gas, that avoids the computational requirement of modeling a large number of composite particles includes 1) quantum molecular modeling of a few particles, 2) determining their available microstates, 3) producing their partition function, 4) generating their statistics, and 5) producing the epicatalytic parameter for the generalized law of mass action.
文摘Application of equations of mixing thermodynamic parameters formulated on the basis of the coexistence theory of metallic melts in Ba-Al, Mg-Al, Sr-Al and Cu-Al melts leads to fruitful results that not only the evaluated mass action concentrations agree well with the measured activities, but also the calculated mixing thermodynamic parameters are quite coincident with the experimental values. Moreover, the calculated mass action concentrations strictly obey the mass action law. The evaluated mixing thermodynamic parameters have very fine regularity: the mixing free energy is composed of standard free formation energies of all compounds and chemical potentials of all structural units at equilibrium; the mixing enthalpy consists of standard formation enthalpies of all compounds; the mixing entropy is composed of standard entropies of all compounds and configuration entropies of all structural units at equilibrium. As the equations of mixing thermodynamic parameters formulated are widely applicable to metallic melts involving compound formation, they can be used as the second practical criterion to determine whether thermodynamic models of metallic melts are correctly formulated.
文摘According to the mass action law and the coexistence theory of metallic melts, the mass action concentrations of Cu-Mg, Bi-Tl 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.
文摘A new curve fitting method with its mathematical models derived from the mass action law is presented which is applicable to several in vitro radioassays including RIA and RBA. Experiments revealed that the robustness of this method is better than the conventional methods like Woolf plot in RBA and 4- parameter logistic plot in RIA. However, the robustness of this method is only relative: in some cases of RIA and RBA, the bias of the results may still be too large to be acceptable. Further improvement is expected to be studied.
