Abstract
High-temperature (1425 to 2750 K) thermodynamic activities of one or both components of twenty-five binary alloys of a group IVB-VIB element (Ti, Zr, Hf, Nb, Ta, or W) with a platinum group element (Ru, Os, Ir, Pd, Pt, or Au) have been determined by equilibrating the alloy with the appropriate carbide and graphite, equilibrating with the nitride and nitrogen gas, or measuring the partial vapor pressure(s) thermogravimetrically or mass spectrometrically. The extraordinary stability of this class of transition metal alloy is attributed to a generalized Lewis-acid-base interaction involving valenced electrons, and the results of these investigations are interpreted within the context of this effect. Among the conclusions made are that a non-spherically-symmetrical crystal field significantly reduces the bonding effectiveness of certain valenced orbitals; the effect of the extent of derealization of these orbitals is also considered.
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Abbreviations
- A :
-
Area of Knudsen cell orifice
- a 1 :
-
Thermodynamic activity of speciesi
- dw/dt :
-
Mass loss per unit time
- E :
-
Relative ionization efficiency
- EPMA:
-
Electron probe microanalysis
- AG° f :
-
Standard free energy of formation
- ΔG i :
-
Partial molal free energy change for transferringi from its standard state (purei) to some mixture.
- Δ•G xs i :
-
Excess partial molal free energy change (= Δ~Gi +TΔ•S id i )
- ΔH° f :
-
Standard enthalpy of formation
- 1 + i :
-
Ion current for species i+
- k i :
-
Mass spectrometer pressure calibration constant for speciesi
- M:
-
Group IVB-VIB element
- M i :
-
Molecular weight of speciesi
- n :
-
Isotopic abundance
- P° :
-
Vapor pressure of speciesi over the pure condensed standard state
- PI:
-
Platinum group element
- R:
-
Ideal gas constant
- Δ•S id i :
-
Ideal (configurational) partial molal entropy change
- X i :
-
Mole fraction of speciesi
- XRD :
-
X-ray diffraction
- ±AX :
-
Uncertainty range corresponding to the reported value /A to the reported value⋅A
- γ i :
-
Electron multiplier gain or activity coefficient for speciesi, as indicated in text
- σ :
-
Ionization cross section
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Formerly Graduate Student Research Assistant, Materials and Molecular Research Division, Lawrence Berkeley Laboratory, and Department of Chemistry, University of California, Berkeley
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Gibson, J.K., Brewer, L. & Gingerich, K.A. Thermodynamics of several lewis-acid-base stabilized transition metal alloys. Metall Trans A 15, 2075–2085 (1984). https://doi.org/10.1007/BF02646841
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DOI: https://doi.org/10.1007/BF02646841