RI 4888 Some Thermodynamic Properties Of Silicon Carbide

Although silicon carbide has been an important manufacture refractory for many years, knowledge of its thermodynamic values has been seriously lacking. In fact, some of the very properties that make it a useful substance, particularly chemical inertness, obstruct determination of its heats of formation and reaction. This paper reports the results of new measurements of the heats of combustion and formation, low-temperature heat capacity, entropy at 298.16°K., and heat-content and entropy increments between 298° and l,800°K. Two varieties of silicon carbide were studied -the common, hexagonal (type II) and cubic. The data are combined to obtain heat and free-energy-of-formation functions, which are given in tabular form. It is shown that the cubic variety is the more stable at temperatures to at least 1,800°K but, because of the inherent difficulties and errors in the heat-of-formation determinations at 298°K, it was not found possible to specify the free-energy difference accurately. The mechanism of silicon carbide formation from silica and carbon is not known and is not ascertainable from thermodynamic data. It appears improbable, however, that it can be a single-step reaction. Some reactions involving silicon monoxide gas and metallic Silicon, as possible intermediates in silicon carbide formation, are considered and shown to be thermodynamically feasible.