In the present study,the modified Sverjensky-Molling equation,derived from a linear-free energy relationship,is used to predict the Gibbs free energies of formation of crystalline phases ofα-MOOH （with a goethite st...In the present study,the modified Sverjensky-Molling equation,derived from a linear-free energy relationship,is used to predict the Gibbs free energies of formation of crystalline phases ofα-MOOH （with a goethite structure）andα-M_2O_3（with a hematite structure）from the known thermodynamic properties of the corresponding aqueous trivalent cations（M^（3＋））.The modified equation is expressed asΔG_（f,M_VX）~0=a_（M_VX）ΔG_（0,M^（3＋））^（0）＋b_（M_VX）＋β_（M_VXγM^（3＋））,where the coefficients a_（M_VX）,b_（M_VX）,andβ_（M_VX） characterize a particular structural family of M_VX（M is a trivalent cation[M^（3＋）]and X represents the remainder of the composition of solid）;γ^（3＋）is the ionic radius of trivalent cations（M^（3＋））;ΔG_（f,M_VX）~0 is the standard Gibbs free energy of formation of M_vX;andΔG_（n,M^（3＋））~0 is the non-solvation energy of trivalent cations（M^（3＋））.By fitting the equation to the known experimental thermodynamic data,the coefficients for the goethite family（α-MOOH）are a_（M_VX）=0.8838,b_（M_VX）=-424.4431（kcal/mol）,andβ_（M_VX）=115（kcal/ mol.（？））,while the coefficients for the hematite family（α-M_2O_3）are a_（M_VX）=1.7468,b_（M_VX）=-814.9573（kcal/ mol）,andβ_（M_VX）=278（kcal/mol.（？））.The constrained relationship can be used to predict the standard Gibbs free energies of formation of crystalline phases and fictive phases（i.e.phases that are thermodynamically unstable and do not occur at standard conditions）within the isostructural families of goethite（α-MOOH）and hematite（α-M_2O_3）if the standard Gibbs free energies of formation of the trivalent cations are known.展开更多
Ba_(1.03)Ce_(0.8)Eu_(0.2)O_(3-α) solid electrolyte with nonstoichiometric composition was prepared by high temperature solid-state reaction. Phase composition, surface and fracture morphologies of the specimen were c...Ba_(1.03)Ce_(0.8)Eu_(0.2)O_(3-α) solid electrolyte with nonstoichiometric composition was prepared by high temperature solid-state reaction. Phase composition, surface and fracture morphologies of the specimen were characterized by using XRD and SEM, respectively. Ionic conduction was researched by gas concentration cell, the performance of hydrogen-air fuel cell was measured in the temperature range of 600～1000 ℃, and compared them with those of BaCe_(0.8)Eu_(0.2)O_(3-α) and Ba_(0.98)Ce_(0.8)Eu_(0.2)O_(3-α). The results indicate that Ba_(1.03)Ce_(0.8)Eu_(0.2)O_(3-α) is a single-phase perovskite-type orthorhombic system. It is a pure proton conductor in the temperature range of 600～1000 ℃ in hydrogen atmosphere, and its proton conduction is superior to that of BaCe_(0.8)Eu_(0.2)O_(3-α) and Ba_(0.98)Ce_(0.8)Eu_(0.2)O_(3-α). It is a mixed conductor of oxide ion and electron hole in oxygen atmosphere. At 1000 ℃, the performance of the fuel cell in which Ba_(1.03)Ce_(0.8)Eu_(0.2)O_(3-α) as electrolyte is higher than that of BaCe_(0.8)Eu_(0.2)O_(3-α) or Ba_(0.98)Ce_(0.8)Eu_(0.2)O_(3-α).展开更多
基金supported by the NSFC(no 40473024 and 40343019)Project of the 11th and 10th Five-Year Research and Development of International Seabed(noDYXM-115-02-1-11,PY105-01-04-13 and DY 105-01-02-1)+2 种基金Project of Key Laboratory of Marginal Sea Geology,Guangzhou Institute of Geochemistry and South China Sea Institute of Oceanology,CAS(no MSGL08-01,MSGLCAS03-4)Specialized Research Fund for the Doctoral Program of Higher Education(no 20040558049)the Fundamental Research Funds for the Central Universities
文摘In the present study,the modified Sverjensky-Molling equation,derived from a linear-free energy relationship,is used to predict the Gibbs free energies of formation of crystalline phases ofα-MOOH （with a goethite structure）andα-M_2O_3（with a hematite structure）from the known thermodynamic properties of the corresponding aqueous trivalent cations（M^（3＋））.The modified equation is expressed asΔG_（f,M_VX）~0=a_（M_VX）ΔG_（0,M^（3＋））^（0）＋b_（M_VX）＋β_（M_VXγM^（3＋））,where the coefficients a_（M_VX）,b_（M_VX）,andβ_（M_VX） characterize a particular structural family of M_VX（M is a trivalent cation[M^（3＋）]and X represents the remainder of the composition of solid）;γ^（3＋）is the ionic radius of trivalent cations（M^（3＋））;ΔG_（f,M_VX）~0 is the standard Gibbs free energy of formation of M_vX;andΔG_（n,M^（3＋））~0 is the non-solvation energy of trivalent cations（M^（3＋））.By fitting the equation to the known experimental thermodynamic data,the coefficients for the goethite family（α-MOOH）are a_（M_VX）=0.8838,b_（M_VX）=-424.4431（kcal/mol）,andβ_（M_VX）=115（kcal/ mol.（？））,while the coefficients for the hematite family（α-M_2O_3）are a_（M_VX）=1.7468,b_（M_VX）=-814.9573（kcal/ mol）,andβ_（M_VX）=278（kcal/mol.（？））.The constrained relationship can be used to predict the standard Gibbs free energies of formation of crystalline phases and fictive phases（i.e.phases that are thermodynamically unstable and do not occur at standard conditions）within the isostructural families of goethite（α-MOOH）and hematite（α-M_2O_3）if the standard Gibbs free energies of formation of the trivalent cations are known.
文摘Ba_(1.03)Ce_(0.8)Eu_(0.2)O_(3-α) solid electrolyte with nonstoichiometric composition was prepared by high temperature solid-state reaction. Phase composition, surface and fracture morphologies of the specimen were characterized by using XRD and SEM, respectively. Ionic conduction was researched by gas concentration cell, the performance of hydrogen-air fuel cell was measured in the temperature range of 600～1000 ℃, and compared them with those of BaCe_(0.8)Eu_(0.2)O_(3-α) and Ba_(0.98)Ce_(0.8)Eu_(0.2)O_(3-α). The results indicate that Ba_(1.03)Ce_(0.8)Eu_(0.2)O_(3-α) is a single-phase perovskite-type orthorhombic system. It is a pure proton conductor in the temperature range of 600～1000 ℃ in hydrogen atmosphere, and its proton conduction is superior to that of BaCe_(0.8)Eu_(0.2)O_(3-α) and Ba_(0.98)Ce_(0.8)Eu_(0.2)O_(3-α). It is a mixed conductor of oxide ion and electron hole in oxygen atmosphere. At 1000 ℃, the performance of the fuel cell in which Ba_(1.03)Ce_(0.8)Eu_(0.2)O_(3-α) as electrolyte is higher than that of BaCe_(0.8)Eu_(0.2)O_(3-α) or Ba_(0.98)Ce_(0.8)Eu_(0.2)O_(3-α).
