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Fluorine as an oxidant in combustion calorimetry

Conference ·
OSTI ID:6625600
Oxygen-bomb calorimetry has been used with some success over the years for the determination of enthalpies of formation ..delta../sub f/H/sub m//sup 0/ of inorganic compounds. This method, however, has a number of drawbacks, the most significant of which is the formation of complicated and ill-defined oxides as reaction products. Substitution of fluorine for oxygen, as the oxidizing gas, eliminates many of those problems. Because of the aggressive nature of fluorine, it can be used to study even the most refractory of materials, but its disadvantages are that it requires very careful handling and special apparatus. A portion of the present paper will discuss the precautions that must be taken, and the special calorimetric equipment that has been constructed. The main scope of the paper, however, is concerned with our recent results obtained for some high-purity chalcogenides. We have performed measurements on both the crystalline and vitreous forms of As/sub 2/Se/sub 3/. The enthalpies of formation have been deduced from the calorimetric enthalpies of fluorination. The following preliminary results at 298.15 K have been obtained and are compared in the paper with published values: ..delta../sub f/H/sub m//sup 0/(As/sub 2/Se/sub 3/, cr) = -(83.7+-4.5) kJ/center dot/mol/sup -1/ and ..delta../sub f/H/sub m//sup 0/(As/sub 2/Se/sub 3/, vit) = -(59.4+-4.3)kJ/center dot/mol/sup -1/. The enthalpy of transition is -(24.3+-3.9)kJ/center dot/mol/sup -1/, only about 60 per cent of the previous literature value. 27 refs., 2 figs., 6 tabs.
Research Organization:
Argonne National Lab., IL (USA)
DOE Contract Number:
W-31109-ENG-38
OSTI ID:
6625600
Report Number(s):
CONF-8809198-1; ON: DE89003626
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400800* -- Combustion
Pyrolysis
& High-Temperature Chemistry
ARSENIC COMPOUNDS
ARSENIC SELENIDES
CALORIMETRY
CHALCOGENIDES
CHEMICAL REACTIONS
COMBUSTION CHAMBERS
ELEMENTS
ENERGY
FLUORINE
FORMATION FREE ENTHALPY
FREE ENTHALPY
GERMANIUM COMPOUNDS
GERMANIUM SELENIDES
HALOGENS
MEASURING INSTRUMENTS
MOLYBDENUM COMPOUNDS
MOLYBDENUM TELLURIDES
NONMETALS
OXIDATION
OXIDIZERS
PHYSICAL PROPERTIES
REFRACTORY METAL COMPOUNDS
SELENIDES
SELENIUM COMPOUNDS
SULFIDES
SULFUR COMPOUNDS
TELLURIDES
TELLURIUM COMPOUNDS
THERMAL ANALYSIS
THERMODYNAMIC PROPERTIES
TRANSITION ELEMENT COMPOUNDS
VANADIUM COMPOUNDS
VANADIUM SULFIDES