Thermodynamic and kinetic studies of some Group III and Group V elements and alloys by solid state electrochemical techniques

Thesis/Dissertation · Wed Oct 01 00:00:00 EDT 1975

DOI:https://doi.org/10.2172/4085203· OSTI ID:4085203

Anderson, Timothy J. ^[1]

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1. Univ. of California, Berkeley, CA (United States)

The Gibbs free energy of forming gallium sesquioxide and indium sesquioxide are measured using a CO₂--CO--O₂ gas reference electrode and calcia stabilized zirconia as the solid electrolyte. The free energies are: δG$$°\atop{f}$$(β-Ga₂O₃(c)) equals -(265,309 ± 152) + (82.47 ± 0.16) (T/K) cal mol^-1 and δG$$°\atop{f}$$(In₂O₃ (c)) equals -(223,160 ± 137) + (79.47 ± 0.12) (T/K) cal mol^-0.1 A solid state galvanic cell is employed to measure gallium activities in Ga--Sb liquid alloys. Results show moderate negative deviations from ideality in the composition range 0.039 less than x/sub Ga/ less than 0.833. Partial molar enthalpies and entropies are calculated, and agree wih calorimetric data. Results are combined with calorimetric data to calculate the liquidus temperatures of the Ga--Sb system, which are in excellent agreement with measurements. Effect of short-range ordering is also investigated. Coulometric titration techniques are used to investigate the solubility and diffusivity of oxygen in liquid indium. Dissolved atomic oxygen is found to follow Henry's law and a saturation solubility of x$$sat\atop{°}$$ equals 3.3 x 10^-3 is determined at 908°K. From a galvanostatic response of an indium electrode, an oxygen diffusivity of 2.2 x 10^-6 cm² s^-1 is found, in good agreement with other available data.

• Research Organization: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
• Sponsoring Organization: US Energy Research and Development Administration (ERDA)
• DOE Contract Number: W-7405-ENG-48
• NSA Number: NSA-33-020743
• OSTI ID: 4085203
• Report Number(s): LBL-4148
• Resource Relation: Other Information: Thesis. Orig. Receipt Date: 30-JUN-76
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
*ANTIMONY ALLOYS- THERMODYNAMIC PROPERTIES
*GALLIUM ALLOYS- THERMODYNAMIC PROPERTIES
*GALLIUM OXIDES- FORMATION FREE ENERGY
*INDIUM OXIDES- - FORMATION FREE ENERGY
*INDIUM- SOLVENT PROPERTIES
*OXYGEN- SOLUBILITY
CALCIUM FLUORIDES
ELECTROLYTES
ELECTROLYTIC CELLS
LIQUID METALS