Influence of chromium and nickel on the dissociation of CO2 on carbon-saturated liquid iron

At 1600 °C, under conditions where the rate was not significantly affected by liquid-phase or gasphase mass transfer, the rate of dissociation of CO₂ was determined from the rate of decarburization of iron-based carbon-saturated melts containing varying amounts of chromium and nickel. The rate was determined by monitoring the change in reacted gas composition with an in-line spectrometer. The results indicate that neither chromium nor nickel had a strong effect on the kinetics of dissociation of CO₂ on the surface of the melt. Sulfur was found to significantly decrease the rate, as is the case for alloys without chromium or nickel, and the rate constant is given by $$k = \frac{{k^0 }}{{1 + K_s a_s }} + k_r $$ where k ⁰ denotes the chemical rate on pure iron, K _s is the adsorption coefficient of sulfur, a _s is the activity of sulfur corrected for Cr, and k _r represents the residual rate at a high sulfur level. The rate constants and adsorption coefficient were determined to be: $$\begin{array}{*{20}c} {k^0 = 1.8 \times 10^{ - 3} mol/cm^2 s atm} \\ {k_r = 6.1 \times 10^{ - 5} mol/cm^2 s atm} \\ {K_s = 330 \pm 20} \\ \end{array} $$ Experiments run at lower carbon contents showed that only a very small quantity of chromium was oxidized, immediately forming a protective layer. However, this oxidation occurred at a higher carbon content (2 pct) than what was expected from the thermodynamics.     

Lattice and grain boundary diffusion of cerium and neodymium in nickel

Diffusion of cerium and neodymium in nickel has been studied by the serial sectioning technique using radioactive tracers¹⁴¹Ce and¹⁴⁷Nd, in the temperature ranges 700° to 1100°C for volume and 500° to 875°C for grain boundary diffusion respectively. Volume diffusivities can be expressed as: $$\begin{gathered} D_{Ce/Ni} = (0.66 \pm 0.18)\exp \left( { - \frac{{60,800 \pm 810}}{{RT}}} \right)cm^2 /\sec \hfill \\ D_{Nd/Ni} = (0.44 \pm 0.13)\exp \left( { - \frac{{59,820 \pm 830}}{{RT}}} \right)cm^2 /\sec \hfill \\ \end{gathered} $$ and grain boundary diffusivities by: $$\begin{gathered} Dg_{Ce/Ni} = 0.11\exp \left( { - \frac{{29,550}}{{RT}}} \right)cm^2 /\sec \hfill \\ Dg_{Nd/Ni} = 0.07\exp \left( { - \frac{{28,580}}{{RT}}} \right)cm^2 /\sec \hfill \\ \end{gathered} $$ Results of volume diffusion have been compared with those calculated from the theories of diffusion based on size and charge difference between the solute and the solvent atoms. Whipple and Suzuoka methods have been used to evaluate the grain boundary diffusion coefficients. Both the methods give similar results.     

Alumina solubility in molten salt systems of interest for aluminum electrolysis and related phase diagram data

The solubility of alumina in molten Na₃AlF₆ containing various amounts of AlF₃, CaF₂, and LiF was determined by measuring the weight loss of a rotating sintered corundum disc. The results were fitted to the following empirical expression: 1 $$ [Al_2 O_3 ]_{sat} = A\left( {\frac{t} {{1000}}} \right)^B $$ where 2 $$ \begin{gathered} A = 11.9 - 0.062[AlF_3 ] - 0.003[AlF_3 ]^2 - 0.50[LiF] \hfill \\ - 0.20[CaF_2 ] - 0.30[MgF_2 ] + \frac{{42[LiF] \cdot [AlF_3 ]}} {{2000 + [LiF] \cdot [AlF_3 ]}} \hfill \\ B = 4.8 - 0.048[AlF_3 ] + \frac{{2.2[LiF]^{1.5} }} {{10 + [LiF] + 0.001[AlF_3 ]^3 }} \hfill \\ \end{gathered} $$ where the square brackets denote weight percent of components in the system Na₃AlF₆-Al₂O₃ (sat)-AlF₃-CaF₂-MgF₂-LiF and t is the temperature in degree Celsius. The standard deviation between the equation and the experimental points in the temperature range from 1050 °C to about 850 °C was found to be 0.29 wt pct Al₂O₃. A series of revised phase diagram data of interest for aluminum electrolysis was derived based on the present work and recently published data for primary crystallization of Na₃AlF₆ in the same systems.     

Interdiffusivities matrix of CaO-Al2O3-SiO2 melt at 1723 K to 1823 K

Ternary oxide mixtures of lime, alumina, and silica were premelted and quenched to produce glassy cylinders. A diffusion couple was selected from the mixtures of six different compositions in such a way that the average composition could be 40 wt pct CaO-20 wt pct A1₂O₃ = 40 wt pct SiO₂. Penetration curves of the components were measured with a X-ray microprobe analyzer. The interdiffusivities matrix defined with the Matano interface has been obtained from 52 successful diffusion runs at 1723 K to 1823 K as follows; 1 $$\begin{gathered} \tilde D_{10 - 10}^{30} = 8.9 \times 10^{ - 11} \exp ( - \frac{{253,700}}{{RT}})(m^2 /s) \hfill \\ \tilde D_{10 - 20}^{30} = - 2.5 \times 10^{ - 11} \exp ( - \frac{{194,300}}{{RT}})(m^2 /s) \hfill \\ \end{gathered} $$ 2 $$\begin{gathered} \tilde D_{20 - 10}^{30} = - 4.0 \times 10^{ - 11} \exp ( - \frac{{177,600}}{{RT}})(m^2 /s) \hfill \\ \tilde D_{20 - 20}^{30} = 6.12 \times 10^{ - 11} \exp ( - \frac{{318,400}}{{RT}})(m^2 /s) \hfill \\ \end{gathered} $$ where symbols, 10, 20, and 30 mean CaO, A1₂O₃, and SiO₂, respectively, and the activation energies are in Joules per mole. The diffusion composition paths obtained are discussed in relation to Cooper’s parallelogram. The composition dependency of the above interdiffusivities is estimated from the quasibinary interdiffusivities in all composition ranges of the present oxide system in liquid state.     

Liquidus temperatures for primary crystallization of cryolite in molten salt systems of interest for aluminum electrolysis

Temperatures for primary crystallization of Na₃AlF₆ in multicomponent electrolyte systems of interest for the aluminum electrolysis process were determined by thermal analysis. The results are presented as binary and quasibinary diagrams and discussed in view of the literature data. An empirical equation describing liquidus temperatures for primary crystallization of Na₃AlF₆ was derived: $$\begin{gathered} t/(^\circ C) = 1011 + 0.50[AlF_3 ] - 0.13[AIF_3 ] - \frac{{3.45[CaF_2 ]}}{{1 + 0.0173[CaF_2 ]}} \hfill \\ + 0.124[CaF_2 ] \cdot [AlF_3 ] - 0.00542([CaF_2 ] \cdot [AlF_3 ])^{1.5} \hfill \\ - \frac{{7.93[Al_2 O_3 ]}}{{1 + 0.0936[Al_2 O_3 ] - 0.0017[Al_2 O_3 ]^2 - 0.0023[AlF_3 ] \cdot [Al_2 O_3 ]}} \hfill \\ - \frac{{8.90[LiF]}}{{1 + 0.0047[LiF] + 0.0010[AlF3]^2 }} - 3.95[MgF_2 ] - 3.95 \hfill \\ \end{gathered} $$ wheret is the temperature in degree Celsius and the square brackets denote the weight percent of components in the system Na₃AlF₆-AlF₃-CaF₂-Al₂O₃-LiF-MgF₂-KF. The composition limitations are [AlF₃] ≈ [CaF₂] ≈ [LiF] < 20 wt pct, [MgF₂] ≈ [KF] < 5 wt pct, and [A1₂O₃] up to saturation.     

Interdiffusivities matrix of CaO-AI2O3-SiO2 melt at 1723 k to 1823 k

Ternary oxide mixtures of lime, alumina, and silica were premelted and quenched to produce glassy cylinders. A diffusion couple was selected from the mixtures of six different compositions in such a way that the average composition could be 40 wt pct CaO-20 wt pct AI₂O₃ = 40 wt pct SiO₂. Penetration curves of the components were measured with a X-ray microprobe analyzer. The interdiffusivities matrix defined with the Matano interface has been obtained from 52 successful diffusion runs at 1723 K to 1823 K as follows; $$ \begin{gathered} \tilde D_{10 - 10}^{30} = 8.9 \times 10^{ - 11} \exp \left( { - \frac{{253,700}} {{RT}}} \right)\left( {m^2 /s} \right) \hfill \\ \tilde D_{10 - 20}^{30} = - 2.5 \times 10^{ - 11} \exp \left( { - \frac{{194,300}} {{RT}}} \right)\left( {m^2 /s} \right) \hfill \\ \tilde D_{20 - 10}^{30} = - 4.0 \times 10^{ - 11} \exp \left( { - \frac{{177,600}} {{RT}}} \right)\left( {m^2 /s} \right) \hfill \\ \tilde D_{20 - 20}^{30} = 6.12 \times 10^{ - 11} \exp \left( { - \frac{{318,400}} {{RT}}} \right)\left( {m^2 /s} \right) \hfill \\ \end{gathered} $$ where symbols, 10, 20, and 30 mean CaO, A1₂O₃, and SiO₂, respectively, and the activation energies are in Joules per mole. The diffusion composition paths obtained are discussed in relation to Cooper’s parallelogram. The composition dependency of the above interdiffusivities is estimated from the quasibinary interdiffusivities in all composition ranges of the present oxide system in liquid state.     

Thermodynamics of iron-aluminum alloys at 1573 K

The activities of iron (Fe) and aluminum (Al) were measured in Fe-Al alloys at 1573 K using the ion-current-ratio technique in a high-temperature Knudsen cell mass spectrometer. The Fe-Al solutions exhibited negative deviations from ideality over the entire composition range. The activity coefficientsγ _Fe, andγ _A1 are given by the following equations as a function of mole fraction (x _Fe,x _Al): 1 $$\begin{gathered} 0< \chi _{A1}< 0.4 \hfill \\ ln \gamma _{Fe} = - 4.511 ( \pm 0.008)\chi _{A1}^2 \hfill \\ ln \gamma _{A1} = - 4.462 ( \pm 0.029)\chi _{Fe}^2 + 0.325( \pm 0.013) \hfill \\ 0.6< \chi _{A1}< 1.0 \hfill \\ ln \gamma _{Fe} = - 4.065 ( \pm 0.006)\chi _{A1}^2 + 0.099( \pm 0.003) \hfill \\ ln \gamma _{A1} = - 4.092 ( \pm 0.026)\chi _{Fe}^2 + 0.002( \pm 0.001) \hfill \\ \end{gathered} $$ The results showed good agreement with those obtained from previous investigations at other temperatures by extrapolation of the activity data to 1573 K.     

Mass-spectrometric determination of activities in Fe−Cr and Fe−Cr−Ni alloys

The Knudsen cell-mass spectrometer combination has been used to study the Fe?Cr system and some Fe?Cr?Ni liquid alloys. The Fe?Cr liquid alloys at 1600°C are found to be essentially ideal when referred to pure liquids as standard states. Phase equilibria over a limited composition range for this system are derived from the behavior of the ion-current ratios. The necessary equations are derived to apply the integration technique to the measured ion current ratios in a ternary system and the method is applied to the Fe?Cr?Ni system at 1600°C. The results are represented, within experimental error, by the following equations: forN _Fe≥0.6, $$\begin{gathered} ln \gamma _{Fe} = - 0.08 N_{Ni}^2 \hfill \\ \ln \gamma _{Cr} = 0.09 - 0.08 N_{Ni}^2 \hfill \\ \ln \gamma _{Ni} = - 0.26 - 0.08(1 - N_{Ni} )^2 \hfill \\ \end{gathered} $$ forN _Fe=0.45, $$\begin{gathered} \ln \gamma _{Fe} = - 0.20 N_{Ni}^2 \hfill \\ \ln \gamma _{Cr} = 0.09 - 0.20 N_{Ni}^2 \hfill \\ \ln \gamma _{Ni} = - 0.19 - 0.20(1 - N_{Ni} )^2 \hfill \\ \end{gathered} $$      

The thermodynamic properties of liquid Fe−Si alloys

The thermodynamic properties of liquid Fe?Si alloys have been determined electrochemically by use of the following galvanic cells: $$\begin{gathered} Cr - Cr_2 O_3 (s)|ZrO_2 (CaO)|Fe - Si(l), SiO_2 (s) \hfill \\ Cr - Cr_2 O_3 (s)|ThO_2 (Y_2 O_3 )|Fe - Si(l), SiO_2 (s) \hfill \\ \end{gathered} $$ The free energy of formation of SiO₂ was measured and is ?139.0 and ?134.3 kcals per mole at 1500° and 1600°C, respectively. The activity coefficients of iron and silicon for the atom fraction of siliconN _Si<0.35 at 1600° and 1500°C can be represented by the quadratic formalism. $$\begin{gathered} \left. {\begin{array}{*{20}c} {log \gamma _{Fe} = - 2.12 N_{Si}^2 } \\ {log \gamma _{Si} = - 2.12 N_{Fe}^2 - 0.22} \\ \end{array} } \right\}1600^ \circ C (2912^ \circ F) \hfill \\ \left. {\begin{array}{*{20}c} {log \gamma _{Fe} = - 2.50 N_{Si}^2 } \\ {log \gamma _{Si} = - 2.50 N_{Fe}^2 - 0.13} \\ \end{array} } \right\}1500^ \circ C (2732^ \circ F) \hfill \\ \end{gathered} $$ The results indicate that an excess stability peak occurs at about the equimolar composition. Combining the heats of solution determined in this study with previous data indicates that the heats also follow the quadratic formalism. The partial molar heats, \(\bar L_{Si} \) and \(\bar L_{Fe} \) , are represented by $$\begin{gathered} \bar L_{Si} = - 31 N_{Fe}^2 - 4 kcals per mole \hfill \\ \bar L_{Fe} = - 31 N_{Si}^2 kcals per mole \hfill \\ \end{gathered} $$ ForN _Si less than 0.35 and by $$\begin{gathered} \bar L_{Si} = - 22 N_{Fe}^2 \hfill \\ \bar L_{Fe} = - 22 N_{Fe}^2 - 7.0 \hfill \\ \end{gathered} $$ forN _Fe less than 0.35. There is an inflection point in the transition region similar to an excess stability peak for the excess free energies. At 1600°C the ThO₂(Y₂O₃) electrolyte exhibited insignificant electronic conductivity at oxygen partial pressures as low as that in equilibrium with Si?SiO₂ (2×10^?16 atm).     

Mass spectrometric determination of activities for alloys with complex vapor species: Bi-Pb and Bi-Tl

For solutions from which complex species vaporize (Bi₂, Si₂, Al₂O, Sb₄, and so forth) new methods of determining the thermodynamic properties from mass spectrometric data are demonstrated. In order to test the feasibility of these new techniques, experiments have been carried out on the liquid Bi-Pb and Bi-Tl systems for which adequate thermodynamic data are available. In evaluating the thermodynamic properties, the ion current ratiosI _Pb ⁺/IBi₂/+ andI _Tl ⁺/IBi₂/+ were employed,e.g. $$\log {\text{ }}\gamma _{{\text{Bi}}} {\text{ = - }}\mathop {\int {\frac{{N_{Pb} }}{{1{\text{ + }}N_{Pb} }}d} }\limits_{N_{Bi} = 1}^{N_{{\text{Bi}}} = N_{Bi} } {\text{ }}\left\{ {{\text{log}}\frac{{{\text{1}}_{{\text{Pb}}}^{\text{ + }} {\text{ }}N_{Bi}^2 }}{{I_{Bi2}^ + {\text{ }}N_{Pb} }}} \right\}$$ Measuring these particular ion current ratios eliminates errors resulting from the fragmentation of the complex vapor species in evaluating the thermodynamic properties. A dimer-monomer technique, which corrects for fragmentation, was also demonstrated. The results using these two independent approaches are in good agreement with each other as well as with previous investigations. The activity coefficients in both systems adhere to the quadratic formalism over large composition ranges,e.g. $$\begin{gathered} \log {\text{ }}\gamma _{{\text{Pb}}} {\text{ = - 0}}{\text{.255 }}N_{Bi}^2 {\text{ }}N_{{\text{Bi}}} {\text{< 0}}{\text{.8}} \hfill \\ \log {\text{ }}\gamma _{{\text{Tl}}} {\text{ = - 0}}{\text{.805 }}N_{Bi}^2 {\text{ }}N_{{\text{Bi}}} {\text{< 0}}{\text{.7}} \hfill \\ \end{gathered} $$      

Determination of standard gibbs energies of formation of Fe2Mo3O12, Fe2Mo3O8, Fe2MoO4, and FeMoO4 of the Fe-Mo-O ternary system and μ phase of the Fe-Mo binary system by electromotive force measurement using a Y2O3-stabilized ZrO2 solid electrolyte

The standard Gibbs energies of formation of Fe₂Mo₃O₁₂, Fe₂Mo₃O₈, FeMoO₄, and Fe₂MoO₄ of the Fe-Mo-O ternary system and the μ phase of the Fe-Mo binary system have been determined by measuring electromotive forces of galvanic cells having an Y₂O₃-stabilized ZrO₂ solid electrolyte. The results are as follows: $$\begin{gathered} \Delta _f G^\circ (FeMoO_4 )/kJ \cdot mol^{ - 1} = - 1053.5 + 0.2983(T/K) \pm 0.4 \hfill \\ Temperature range: 1112 to 1339 K \hfill \\ \Delta _f G^\circ (Fe_2 Mo_3 O_8 )/kJ \cdot mol^{ - 1} = - 2347 + 0.6814(T/K) \pm 1 \hfill \\ Temperature range: 1112 to 1339 K \hfill \\ \Delta _f G^\circ (Fe_2 Mo_3 O_{12} )/kJ \cdot mol^{ - 1} = - 2993 + 0.9105(T/K) \pm 2 \hfill \\ Temperature range: 1040 to 1145 K \hfill \\ \Delta _f G^\circ (Fe_{0.58} Mo_{0.42} )/kJ \cdot mol^{ - 1} = - 18.7 + 0.0117(T/K) \pm 0.1 \hfill \\ Temperature range: 1162 to 1223 K \hfill \\ \Delta _f G^\circ (Fe_2 MoO_4 )/kJ \cdot mol^{ - 1} = - 1174 + 0.342(T/K) \pm 1 \hfill \\ Temperature range: 1243 to 1466 K \hfill \\ \end{gathered} $$ where the standard pressure is 1 bar (100 kPa).     

Enthalpy of mixing of liquid Ni-Zr and Cu-Ni-Zr alloys

The partial (Δ and the integral (ΔH) enthalpies of mixing of liquid Ni-Zr and Cu-Ni-Zr alloys have been determined by high-temperature isoperibolic calorimetry at 1565 ± 5 K. The heat capacity (C _p) of liquid Ni₂₆Zr₇₄ has been measured by adiabatic calorimetry (C _p=53.5±2.2 J mol⁻¹ K⁻¹ at 1261±15 K). The integral enthalpy of mixing changes with composition from a small positive (Cu-Ni, ΔH (x _Ni=0.50, T=1473 to 1750 K)=2.9 kJ mol⁻¹) to a moderate negative (Cu-Zr; ΔH(x _Zr=0.46, T=1485 K)=−16.2 kJ mol⁻¹) and a high negative value (Ni-Zr; ΔH(x _Zr=0.37, T=1565 K)=−45.8 kJ mol⁻¹). Regression analysis of new data, together with the literature data for liquid Ni-Zr alloys, results in the following relationships in kJ mol⁻¹ (standard states: Cu (1), Ni (1), and Zr (1)):for Ni-Zr (1281≤T≤2270 K),

Iron redox equilibria in CaO-Al2O3-SiO2 and MgO-CaO-Al2O3-SiO2 slags

Measurements have been made of the ratio of ferric to ferrous iron in CaO-Al₂O₃-SiO₂ and MgO-CaO-Al₂O₃-SiO₂ slags at oxygen activities ranging from equilibrium with pCO₂/pCO≈0.01 to as high as air at temperatures of 1573 to 1773 K. At 1773 K, values are given by $\begin{gathered} \log {\text{ }}\left( {\frac{{Fe^{3 + } }}{{Fe^{2 + } }}} \right) = 0.3( \pm {\text{ }}0.02){\text{ }}Y + {\text{ }}0.45( \pm {\text{ }}0.01){\text{ }}\log \hfill \\ \left( {\frac{{pCO_2 }}{{pCO}}} \right) - 1.24( \pm {\text{ }}0.01) \hfill \\ \end{gathered} $ where Y=(CaO+MgO)/SiO₂, for melts with the molar ratio of CaO/SiO₂=0.45 to 1.52, 10 to 15 mol pct Al₂O₃, up to 12 mol pct MgO (at CaO/SiO₂≈1.5), and with 3 to 10 wt pct total Fe. Available evidence suggests that, to a good approximation, these redox equilibria are independent of temperature when expressed with respect to pCO₂/pCO, probably from about 1573 to 1873 K. Limited studies have also been carried out on melts containing about 40 mol pct Al₂O₃, up to 12 mol pct MgO (at CaO/SiO₂≈1.5), and 3.6 to 4.7 wt pct Fe. These show a strongly nonideal behavior for the iron redox equilibrium, with $\frac{{Fe^{3 + } }}{{Fe^{2 + } }} \propto \left( {\frac{{pCO_2 }}{{pCO}}} \right)^{0.37} $ The nonideal behavior and the effects of basicity and Al₂O₃ concentration on the redox equilibria are discussed in terms of the charge balance model of alumino-silicates and the published structural information from Mössbauer and NMR (Nuclear Magnetic Resonance) spectroscopy of quenched melts.     

Kinetics and mechanism of the reduction of molten nickel sulfide by hydrogen

The kinetics and mechanism of the reduction of M₃S₂ by hydrogen have been investigated between 1133° and 1300°C. When high flow rates of hydrogen and argon or helium bubbling through the melt are maintained the rate-determining step is a chemical process which can be expressed by a rate law of the form $$\begin{gathered} r_{H_2 S} = k_{expt} (N_S - \alpha )^2 p_{H_2 }^{1/2} \hfill \\ p_{H_2 } \geqslant 0.88atm \hfill \\ \end{gathered} $$ where k_expt = 85.1 atm^-1/2 min^-1, α = 0.17 at 1250°C. The experimental activation energy for this process is 20.1 ±3.0 kcal per mole. These results are discussed in terms of possible catalysis by nickel.     

Thermodynamic behavior in binary metallic solutions

The applicability of Krupkowski’s formalism $$\begin{gathered} ln \gamma _1 = \omega \left( T \right)\left( {1 - X_1 } \right)^m \hfill \\ ln \gamma _2 = \omega \left( T \right)\left[ {\left( {1 - X_1 } \right)^m - \frac{m}{{m - 1}}\left( {1 - X_1 } \right)^{m - 1} + \frac{1}{{m - 1}}} \right] \hfill \\ \end{gathered} $$ in interpreting experimental data is shown for several binary systems. Both dilute and concentrated solutions are considered. In dilute solutions (Henry’s law region) these equations exclude constant values of the activity coefficients. These formulae withm>1 satisfy Raoults law and Henry’s law as limiting cases. However, experimental data indicate that only in two systems, namely Zn-Sn and Zn-Bi,γ _Zn ⁰ =γ _Zn over a finite composition range. Whenm is close to unity, as is the case for the Zn-Sn and Zn-Bi systems Raoult’s law is not satisfied untilX _Zn is infinitesimally close to unity. Data for concentrated zinc solutions for both systems support this conclusion. A comparison of Krupkowski’s method with Darken’s quadratic formalism was also carried out, and it was shown that both methods give similar results whenm=2.     

Controversy on the free energy of formation of CaO—Additional evidence in support of thermochemical data

The standard free energies of formation of CaO derived from a variety of high-temperature equilibrium measurements made by seven groups of experimentalists are significantly different from those given in the standard compilations of thermodynamic data. Indirect support for the validity of the compiled data comes from new solid-state electrochemical measurements using single-crystal CaF₂ and SrF₂ as electrolytes. The change in free energy for the following reactions are obtained: $$\begin{gathered} CaO + MgF_2 \to MgO + CaF_2 \hfill \\ \Delta G^ \circ = - 68,050 - 2.47 T( \pm 100) J mol^{ - 1} \hfill \\ SrO + CaF_2 \to SrF_2 + CaO \hfill \\ \Delta G^ \circ = - 35,010 + 6.39 T( \pm 80) J mol^{ - 1} \hfill \\ \end{gathered} $$ The standard free energy changes associated with cell reactions agree with data in standard compilations within ±4 kJ mol^?1. The results of this study do not support recent suggestions for a major revision in thermodynamic data for CaO.     

Electrical conductivity of molten cryolite-based mixtures obtained with a tube-type cell made of pyrolytic boron nitride

A pyrolytic boron nitride tube-type cell was used to measure the electrical conductivity for molten cryolite, for binary mixtures of cryolite with Al₂O₃, AlF₃, CaF₂, KF, Li₃AlF₆, and MgF2, and for ternary mixtures Na₃AlF₆-Al₂O₃-CaF₂ (MgF₂) and Na₃AlF₆-AlF₃-KF (Li₃AlF₆). The cell constant was about 40 cm^?t. The temperature and concentration dependence of the conductivity in the investigated concentration range was described by the equation $$\begin{gathered} \kappa /S cm^{ - 1} = 7.22 exp\left( { - 1204.3/T} \right) - 2.53\left[ {Al_2 O_3 } \right] - 1.66\left[ {AlF_3 } \right] \hfill \\ - 0.76\left[ {CaF_2 } \right] - 0.206\left[ {KF} \right] + 0.97\left[ {Li_3 AlF_6 } \right] - 1.07\left[ {MgF_2 } \right] \hfill \\ - 1.80\left[ {Al_2 O_3 } \right]\left[ {CaF_2 } \right] - 2.59\left[ {Al_2 O_3 } \right]\left[ {MgF_2 } \right] \hfill \\ - 0.942\left[ {AlF_3 } \right]\left[ {Li_3 AlF_6 } \right] \hfill \\ \end{gathered} $$ whereT represents the temperature in Kelvin and the brackets represent the mole fractions of the additions. The standard deviation was found to be 0.026 S cm^?1 (～1 pct). For practical reasons, it is often desired to express composition in weight percent. In that case, it holds that $$\begin{gathered} \ln \kappa = 1.977 - 0.0200\left[ {Al_2 O_3 } \right] - 0.0131\left[ {AlF_3 } \right] - 0.0060\left[ {CaF_2 } \right] \hfill \\ - 0.0106\left[ {MgF_2 } \right] - 0.0019\left[ {KF} \right] + 0.0121\left[ {LiF} \right] - 1204.3/T \hfill \\ \end{gathered} $$ whereT represents the temperature in Kelvin and the brackets denote the concentration of the additives in weight percent. However, in this case, the maximum relative error of the conductivity equation can reach up to 2.5 pct.     

Solubility product of aluminum nitride in 3 percent silicon iron

The solubility product of aluminum nitride in 3 pct silicon iron was determined experimentally from 1273 to 1473 K with results described by the equation $$\begin{gathered} \log [pct \underline {Al} _{\alpha (3Si) } pct \underline N _{\alpha (3Si)} ] \hfill \\ = {\text{--11,900/}}T + 3.56 \hfill \\ \end{gathered} $$ whereT is in kelvins and concentrations are in weight percent. In the experiments the equilibrium distribution of nitrogen between purified gamma iron (fcc) and 3 pct silicon alpha iron (bcc) was determined between 1273 and 1523 K.