An assessment of high-temperature mass spectrometry and of sources of inaccuracy is made. Experimental, calculated, and estimated cross-sections for ionization of atoms and inorganic molecules typically present in high-temperature vapors are summarized. Experimental cross-sections determined for some 56 atoms are generally close to theoretically calculated values, especially when excitation–autoionization is taken into account. Absolute or relative cross-sections for formation of parent ions were measured for ca. 100 molecules. These include homonuclear diatomic and polyatomic molecules, oxides, chalcogenides, halides, and hydroxides. Additivity of atomic cross-sections supplemented by empirical corrections provides fair estimates of molecular cross-sections. Causes of uncertainty are differences in interatomic distances and in shapes of potential energy curves (surfaces) of neutral molecules and of molecular ions and tendency toward dissociative ionization in certain types of molecules. Various mass spectrometric procedures are described that render the accuracy of measured thermodynamic properties of materials largely independent of ionization cross-sections. This accuracy is comparable with that of other techniques applicable under the conditions of interest, but often only the mass spectrometric procedure is appropriate at high temperatures.

The sublimation of hexagonal SiC has been studied under equilibrium conditions. The predominant gaseous species above SiC are Si, SiC2, and Si2C. By combining the heat of formation of gaseous Si from solid SiC and the known standard heat of formation of SiC, a value of 113 kcal/g atom is obtained for the heat of sublimation of Si at 298°K. From the measured partial pressures, using estimated free energy functions, dissociation energies for Si2, Si3, SiC, SiC2, Si2C, Si2C2, Si2C3, and Si3C are calculated and compared with previously known dissociation energies for group IV B molecules.

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The vaporization behavior of the systems boron—carbon and boron—carbon—silicon has been studied with a mass spectrometer. In addition to the gaseous species characteristic of graphite, silicon carbide and boron, the molecules BC2, B2C, BCSi, BSi2, BC, and BSi were identified and their atomization energies measured. The values are: 294, 254, 247, 174, 106, and 68 kcal/mole, respectively. The atomization energies of SiC, Si2C, and SiC2 have been redetermined.

High-temperature mass spectrometry (hitherto at temperatures between I000 and 2500 " K and at pressures between 10-3 and 10-12 atm) has already made possible the identiJication of many previously unknown and unpredicted diatomic and polyatomic molecular species. The present paper deals with the investigation of many oxides, of halides, and of carbon molecules and intermetallic molecules. An apparatus for the production and investigation of molecular beams is described. Knudsen cells permit the production of molecular beams under equilibrium conditions; in special cases the "doubleoven" type of Knudsen cell is used. Thermodynamic and kinetic quantities such as d H; values, dissociation energies, and ionization cross sections of the species investigated are given.