The vaporization behavior of the boron-sulfur system has been studied mass spectrometrically with a glassy, sulfur-rich B2S3 sample, a stoichiometric B2S3 sample, a stoichiometric B2S3 -Zn mixture, and a FeS-B-Zn mixture. Glassy B& gave the most intense and most complicated spectra; the stoichiometric BsS3 sample, the stoichiometric B2S3-Zn mixture, and the early stages of the FeS-B-Zn mixture gave, in the temperature range 400-650 O, indistinguishable spectra that were intermediate in intensity and complexity; and the ZnS-B system, to which the FeS-B-Zn mixture converted in later stages, gave the simplest spectra with the lowest intensities. Ion intensities, appearance potentials, metastable transitions, fragmentation patterns, and temperature dependences are used to show that the parent ions from stoichiometric BZS3 were polymers of B2S3(g) and that BZS3(s) vaporizes congruently. Sulfur-rich samples vaporize incongruently to give polymers of both BSz(g) and BzS3(g). Sulfurdeficient systems also give B2S2(g). Polysulfide bonds are suggested as the cause of the higher volatility and lower melting points of the sulfur-rich samples.he discovery of the gaseous ions of polymeric com-
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