Extractive Metallurgy Division - Sulfur Pressure Variation of Molybdenum Disulfide at 1100°C (TN)

PARRAVANO and Malquori' studied the equilibrium of H2S-Hz with molybdenum and its lowest sulfide which they believed to be MoS2. Mc Cabe' has shown that its composition is actually Mo2S3 and determined its dissociation pressure by means of Knud-sen effusion measurements. Stubbles and Richard- son3 have recently studied the equilibrium of gas mixtures of H2S-HZ with the two-phase solid mixtures of Mo-MozS3 and Mo2S3-MoS2. The latter investigators found that M02s3 deviated slightly from the stoichiometric composition, but they did not determine the homogeneous region of the disulfide phase. Morimoto and Kullerud, studied the Mo-S system by quenching, microscope, and X-ray methods and concluded that the disulfide is stoichiometric. The present investigation was concerned with the measurement of the sulfur vapor pressure variation with composition at 1100°C in the homogeneous region of "MoS2". These measurements were made by reacting: 1) molybdenum powder (99.97 pct Moj with sulfur vapor, and 2) MoS1.g9 (formed by reaction of Mo + H2S) with sulfur vapor in a quartz capsule. Conditions were controlled to form an equilibrated phase within the homogeneous region of the disulfide. The quartz capsule was sealed off initially under a vacuum and the residual gases were gettered by titanium powder contained in one end of the capsule. A mixture of Mo + S or MOS,., + S was in the other end. The section containing the titanium powder was heated for 24 hr at 700°C and then removed by flame sealing. The end of the capsule containing the charge was then heated to 1100°C. The other end of the capsule was maintained at a temperature which would produce the desired sulfur pressure in the capsule (liquid sulfur distilled from the charge mixture was retained in this end). After equilibration, the capsule was removed from the heating assembly and rapidly air-cooled. It is assumed that equality existed between the total sulfur pressures (PT) in the two ends of the capsule and not between the partial pressures of the different molecular species (S, SZ, Three separately controlled heating elements were used to maintain the proper temperature gradient over the length (approximately 12 in.) of the capsule. A thermocouple-Wheelco "Capacitrol" system was used for temperature control of the two end heating elements within 2"C. The center heating element was controlled directly by a " Power -stat". Separate controlling and measuring thermocouples were used for both end heating elements. Pt-Pt(l0 pct Rh) thermocouples were used for 1100°C and Chromel-Alumel thermocouples were used for lower-temperature control and measurement of the assembly. Silver foil was wrapped around the end of the capsule containing the liquid sulfur to insure a constant temperature zone. The thermal gradient over the entire length of the capsule was measured to: 1) ascertain that the length of the constant temperature zone of the liquid-sulfur end and the sulfide end was sufficient, and 2) ascertain that the liquid-sulfur zone was the zone of lowest temperature. The data obtained in this investigation are shown in Fig. 1 and Table I. The total sulfur pressure (PT) and p(S2) were calculated from the data of Braune et UZ.~ The compositions of the equilibrated disul-