Kinetics of the thermal dissociation of Co₄S₃ under reduced pressure

Abstract

Kinetics of the thermal dissociation of Co₄S₃ were investigated under reduced pressures of 5 × 10^-2 and 1.5 × 10^-4 mm Hg in the temperature range 1120° to 1405° C. The initial 10 pct dissociation was found to take place in accordance with a linear rate law, with activation energies of 20 and 17 kcal per mole under low and high vacuums, respectively. Subsequent dissociation up to about 35 pct was observed to be parabolic in nature, with activation energies of 38 and 40 kcal per mole under the respective vacuums. Further dissociation up to about 90 pct was found to fit into another linear rate law, with activation energies of 47 and 49 kcal per mole under the reduced pressures of 5 × 10^-2 and 1.5 × 10^-4 mm Hg, respectively. Beyond 90 pct, the dissociation was found to be very sluggish. These results have been interpreted with the help of the Co-S phase diagram. It has also been possible to achieve more than 99 pct dissociation of Co₄S₃ in 2 hr at 1405° C under low vacuum or 1355° C under high vacuum.