FREE ENERGY OF FORMATION OF Na_2SnO_3 BY EMF MEASUREMENT USING β-ALUMINA SOLID ELECTROLYTE CELL

A β”/β-Al_2O_3 solid electrolyte was prepared and used in a Na conentration galvanic cell: (-)O_2(in Ar),SnO_2,Na_2SnO_3|β"/β-Al_2O_3]NaCrO_2,Cr_2O_3,O_2(in Ar)(+).The emf measurements were carried out in temperature range of 912—1223 K:E=652.1— 0.2092 T+2.3(mV).Using this equation and cited free energies of formation of NaCrO_2, Cr_2O_3 and SnO_2,the molar free energy of formation of Na_2 SnO_3 may be calculated by ΔG°=-1050+0.2544 T±5.4(kJ mol^(-1)).

Electrochemical determination of Gibbs free energy of formation of magnesium ferrite

The standard Gibbs free energy of formation of magnesium ferrite was determined by means of two types of solid state electrochemical cells： one using MgZr4（PO4）6 （MZP） as the solid electrolyte and the other using CaF2 as the solid electrolyte. The first cell was operated in the range of 950 to 1100 K. The second cell was operated in the range of 1125 to 1200 K. The reversibility of the cell EMFs was confirmed by microcoulometric titration. The Gibbs energy changes of magnesium ferrite relative to component oxides were calculated based on EMF measurements and are given by following expressions, respectively： AG1 = -3579-15 T （J/mol） and AGⅡ =6258-24.3 T （J/mol）. The results obtained from two different cells are consistent with each other. The results also are in agreement with Rao＇ s and Tretjakov＇s data in the measured temperature range. When the Gibbs free energies of formation of MgO and Fe203 were substituted in the reaction, the Gibbs free energies of formation of MgFe204 was obtained in two temperature ranges and the for mations are shown as follows： AG 1Formation =-1427394＋360.5 T （J/mol） and AGⅡ Formition =-1417557＋351.2 T （J/mol）.

FREE ENERGIES OF FORMATION FOR ELECTROCHEMICALLOY ALLOYED Y-Cu SYSTEM

The electrochemical alloying of Y-Cu system in molten NaCl-KCl-YCl_3 has been investi- gated.The free energy changes of the formation reactions of the intermetallic compounds,in- cluding YCu_6 ,YCu_4 YCu_2 ,Yfu(973—103 K),were determined by means of electrode potential-time curves of the working electrode after potentiostatic electrolysis.The results in- dicate that the potential-time method is simple and reliable.

The Quasi-Parabolic Regulation of the Standard Free Energies of Formation of Binary Intermediate Compounds

In this paper it has theoretically proved that the relationship of the molar atomic standard free energies of formation of binary intermediate compounds to the molar fraction of component is a quasi-parabola which is called a quasi-parabolic regula- tion.

Electrochemical formation of holmium-cobalt alloys

The electrochemical formation processes of holmium-cobalt alloys on cobaltcathode in molten HoCl_3-KCl were investigated by cyclic voltammetry and open current potential-timecurve alter potentiostatic electrolysis. The structure of Ho-Co alloys' films deposited on cobaltelectrode by potentiostatic electrolysis was characterized by X-ray diffraction. The standard Gibbsfree energies of formation for the intermetallic compounds of Ho and Co were determined. Thediffusion coefficient and diffusion activation energy of Ho atom in the alloy phase were calculatedto be 10^(-10) -10^(-11) cm^2/s and 96.0 kJ/mol, respectively, from the current-time curve atpotential step.

Calculation and Verification for the Thermodynamic Data of 3CaO·3Al_2O_3·CaSO_4

Calcium sulfoaluminate,3CaO·3Al2O3·CaSO4,has been widely recognized in the realms of high-temperature combustion and cement chemistry.However,the lack of relevant thermodynamic data limits the progress of its research and development.Through comparative calculations using several different approaches,we obtain the thermochemical properties of 3CaO·3Al2O3·CaSO4 in this work,such as its standard formation enthalpy,Gibbs free en- ergy of formation,entropy,and molar heat capacity.With these fundamental data,thermodynamic calculations become possible for reactions involving this mineral.It is found that some reactions proposed in literature to generate this mineral may not proceed thermodynamically.

THERMODYNAMICS OF Cu-Ce-I(I=Al,Si,Ti,Fe)LIQUID SOLUTIONS

The iso-activity of[Ce]of samples reached in multiple-hole-graphite crucibles by controlling the oxygen potential through the reaction 2[Ce]+3CO=Ce_(2)O_(3)+3C.Combining conjugate gradient method of solving ill-conditioned equations,the activity interaction coeffients between Ce and Al.Si,Ti and Fe alloying elements were determined.The equilibrium constant of the reaction 2[Ce]+3[O]=Ce_(2)O_(3)and the standard free energy of formation of Ce203 in liquid Cu were obtained at 1.200 C.

Thermodynamic properties of LaCrO_3

The nano powders of LaCrO3 were prepared by a sol-gel route. The heat capacity of LaCrO3 nano powders from 350 to 550 K was measured by DSC method and expressed as： Cpa2CrO3） （±0.112） = 166.844 - 8.500 ×10^-3T- 1.022×10^6T^-2 （J/（mol.K）） （350-550 K）. An EMF measurement assembly was developed with CaF2 as an electrolyte for the galvanic cell. From measured EMF data of the reversible cell, （-） PL La2O3, LaF3, O2 （1 atm）lCaF2O2（1 atm）, LaF3, LaCrO3, Cr2O3, Pt（＋）, and the relevant value of Gibbs free energy, the Gibbs free energy of formation of LaCrO3 was calculated from 700 to 885 K： △G ФaLaCrO3 = -1555.364 ＋ 0.354T （kJ/mol） （700-885 K）. And the Gibbs free energy change of reaction from simple oxides La2O3 and Cr2O3 was calculated to be： AG f Oox（LaCrO3） = -94.758 ＋ 8.530×10^-2T（kJ/mol） （700-885 K）.

Electroreduction of Ho^(3+) on Nickel Cathode in Molten KCl-HoCl_3

The cyclic voltammetry, open current potential-time curve after potentiostatic electrolysis, the currenttime curve at potential step, XRD, EDAX and EPMA were used to study the electrode process of Ho3+ reduction on nickel electrode in molten KCI-HoC13 and the phases of surface alloy layer. The Ho-Ni alloys were deposited when Hos+ was reduced on the nickel electrode. The free energies of formation for the intermetallic compounds between Ho and Ni, the diffusion coefficients and diffusion activation energy of Ho astom in the alloy phase were determined.

High Temperature Thermodynamics of RE(La,Ce,Pr,Y,Tb)-S-F Systems

The compounds of RESF. RE = La. Ce. Pr, Y and Tb, were made from RE_2S_3 and REF_3 by high tem-perature solid reaction. The Gibbs standard free energies of formation of RESF were measured by galvaniccell technique by using CSZ as solid electrolyte. The results of this work together with the Gibbs standardfree energies of formation ol RE,S. . REzSa and REFa were used to determine the phase diagrams ofRESF systems in this paper.