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 .

THE APPLICATION OF THE LAW OF MASS ACTION IN COMBINATION WITH THE COEXISTENCE THEORY OF SLAG STRUCTURE TO THE MULTICOMPONENT SLAG SYSTEMS

It is shown by the the law of mass action in combination with the coexistence theory of slag structure that KMn n =NMno /(NFeo [%Mn] does not change with basicities and maintains constant at constant temperature; the oxidizing capabilities of multicomponent slag systems containing CaO, MgO etc., can be expressed by NFe tO =NFeO + 6NFe2 O3 + 8NFe3O4; the desulfurizing capabilities of various basic oxides for multicomponent slag systems can be calculated by Ls=8(KCaSNCaO+KMgsNMgo +KFeSNFeO)∑n/[%O]; the dephosphorizing capabili- ties of CaO-MgO-FeO-FeO O3-P2 O5 as well as CaO-FeO-Fe2 O3-A12 O3-P2 O5 molten slags expressed respectively by Lpo=(%P2O5)/[P]2 = 141.94[%O]5∑nK00(1 + K5N2Cao + K6N3CaO + K7N4CaO + K8N2MgO + K9N3MgO + K10N3FeO + K11N4Feo); LPO=(%P2O5)/[P]2= 141.94[%O]5∑nK00(1 + K10N2CaO+ K11N3CaO+ K12N4CaO + K13N3FeO + K14N4FeO) have good agreement with practical values.

APPLICABILITY OF THE MASS ACTION LAW IN COMBINATION WITH THE COEXISTENCE THEORY OF METALLIC MELTS INVOLVING COMPOUND TO BINARY METALLIC MELTS

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.

Determination of thermodynamic properties in full composition range of Ti-Al binary melts based on atom and molecule coexistence theory

The results of predicting thermodynamic properties in the full composition range of Ti-Al binary melts in a temperature range from 1973 to 2273 K were obtained by coupling with the developed thermodynamic model for calculating mass action concentration N_i of structural units in Ti-Al system based on the atom and molecule coexistence theory（AMCT）. Temperature dependence of the activity coefficients of Ti and Al in natural logarithmic form in the infinitely dilute solution（0x_（Ti）0.01） of Ti-Al binary melts was also determined from the calculated activity coefficients of Ti and Al at temperatures of 1973, 2073, 2173, and 2273 K. The standard molar Gibbs free energy change of dissolving pure liquid element i（l） for forming 1%（mass fraction） element i in Ti-Al binary melts further was deduced. With the aid of this model, meanwhile, the determined excess thermodynamic properties, such as the excess molar mixing Gibbs free energy/entropy/enthalpy were also calculated.

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-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.

Controlling oxygen content in electro-slag remelting steel by optimizing slag-steel reaction process

The thermodynamic equilibrium of deoxidation reactions between molten slag and steel was calculated using a slag-steel coupling thermodynamic model and the mass conservation model based on the ion-molecular coexistence theory.The study focused on the effects of slag composition and deoxidizer type on the oxygen content of low alloy steel during the electroslag remelting(ESR)process.The measured and predicted values of the oxygen content in remelted ingots,and the contents of FeO and MnO in slags were compared and analyzed.Results show that the measured content of total oxygen has a certain correlation with the trend of dissolved oxygen predicted by the model when using Ca-Si alloys as deoxidizer,but it is not correlated with the trend of dissolved oxygen predicted by the model when using Al as deoxidizer.The deoxidation mechanisms of Ca-Si and Al are different.Ca-Si alloy directly reacts with FeO and MnO in slag to reduce the oxygen potential of slag,hence it can inhibit the transfer of oxygen from the slag to molten steel.While,when Al deoxidizer is used,the oxygen content in steel is mainly reduced through floating up the alumina inclusions.Compared to Al,utilizing Ca-Si alloy as a deoxidizer is more effective in reducing the oxygen content and the amount of inclusions in ESR ingot.

A thermochemical model description of CaO_(2)-SiO2-Al_(2)O_(3) silicate system

A thermochemical model based on the ion and molecule coexistence theory(IMCT)was developed to calculate thermodynamic data in the CaO-SiO_(2)-Al_(2)O_(3) slag system,considering the influential role of oxide activities on the thermodynamic properties of slags.Using this model,iso-activity contours were obtained for oxide components CaO,SiO_(2) and Al2O3 in this system at temperatures of 1,873 K and 1,773 K.When compared with the IMCT model,it is found that the predicted activities of oxide components in the CaO-SiO_(2)-Al_(2)O_(3) system using the model developed in this study better matches experimental data from literature in terms of both trend and numerical value.Therefore,the model developed in this study can serve as a robust modeling tool for metallurgical processes,and the thermodynamic data predicted by this new model can be used to improve the metallurgical technology.

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.

Thermodynamic model of lead oxide activity in PbO-CaO-SiO_2-FeO-Fe_2O_3 slag system

According to the ion and molecule coexistence theory, a thermodynamic model of lead oxide activity in PbO-CaO-SiO2-FeO-Fe2O3 slag system was established at the temperature of 1273-1733 K. The activities of Pb O in slag were calculated, and their equal activity curves were plotted. The influences of slag basicity Q, iron oxide rate R and temperature T on activity NPb O and activity coefficient γPbO were also investigated. Results show that the calculated values of γPb O are in good agreement with the reported experimental data, showing that the model can wholly embody the slag structural characteristics. NPbO departures positively from Raoult values, and increases with increasing Pb O content in slag but changes little with T. γPbO increases with increasing Q, and goes through the maximum with increasing R for basic slag（Q0.3）. Results can be applied to the thermodynamic research and operational optimization of modern lead smelting technologies.

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.

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

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.

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.

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.

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.

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 Parameter of Binary Metallic Melt Involving Compound Formation

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.

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.

Experiment of Microwave Heating on Self-Fluxing Pellet Containing Coal

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.

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.

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.