RI 3341 Progress Reports - Metallurgical Division - 19. Thermodynamic Studies

"In an earlier consideration of the vapor pressure of iron 3/ it was found necessary to estimate the specific heat of gaseous iron to write satisfactory free-energy-of-vaporization equations for the several forms of iron. That the specific heat of gaseous iron will exceed greatly the classical value of Cp = 4.967 calories per gram-mole per degree is evident from even a cursory Lamination of its spectrum. The two lowest energy states are separated by only 416 cm-1, which is small enough so that the second state is effective, theoretically, at below room temperature. Such phenomena are by no means uncommon, but, while they have been recognized with substances that ordinarily are encountered as gases, classical gaseous specific--heat values still are used, often without question, for the vapors of metals and other elements that are solids under ordinary conditions. The following calculations for iron and copper gases are presented to illustrate the sort of deviations from classical values that are encountered with metal gases.The methods employed in calculating from spectroscopic data of thermodynamic quantities such as specific heat, entropy, and free energy have been described, in detail by Giauque 4/ and others. These will be briefly reviewed here. It is customary to separate the translational energy of a molecule from the rotational, vibrational, and electronic energies. In the case of monatomic gases, only translational and electronic Energies are involved. The classical expression for the specific heat of a mona¬tomic gas, Cp = 4.967, deals only with energy stored in the molecule as translational energy and consequently is valid only in temperature ranges in which no appreciable number of molecules undergoes a change in electronic state."