Thermodynamic calculation, ab initio molecular dynamics(AIMD) and vacuum decomposition experiments were performed to study the volatilization behaviors of Mo and S from molybdenite concentrate by vacuum decomposition. In thermodynamic calculation, starting decomposition temperatures of reactions were calculated, and saturated vapor pressures of Mo, S and Mo S2 were also analyzed. In AIMD, geometries of the Sn(n≤8), Mom(m≤8) and MomSn(m+n≤8) clusters have been optimized using density functional theory(DFT) with generalized gradient approximation(GGA). And these clusters were simulated in DFT with Cambridge Sequential Total Energy Package(CASTEP) code of Material Studio software. Structures and stabilities of these clusters before and after molecular dynamics simulations were discussed, and diffusion coefficients were also calculated. In vacuum decomposition experiments, relationship between heat preservation time and volatilization rate of Mo and S was obtained, while the constant temperature and chamber pressure were 1823 K and 5–35 Pa, respectively. Above all, both the theoretical and experimental results showed that volatilization behaviors of Mo and S during vacuum decomposition process of molybdenite concentrate were as follows: Mo could partly evaporate into the condensate in the form of clusters, and S could easily evaporate into the condensate.
To make sure the intermediate products of the carbothermic reduction of Al2O3 process, such as Al4CO4, Al2CO and Al4C3,and the interaction of AlCl, AlCl2, AlCl3 with Al4CO4, Al2CO and Al4C3, respectively, thermodynamic analyses were used to study the chloride reaction production of them under the vacuum situation. The stable structures and electronic properties of AlCl, AlCl2 and AlCl3 adsorbed on Al4CO4, Al2CO and Al4C3 were calculated by first-principles calculations by the CASTEP module in the Materials Studio program. The results show that the AlCl3 and AlCl2 molecules have decomposed on the plane of Al4C3（001）, while there are no obvious decomposition of AlCl3 and AlCl2 on Al4CO4（001） and Al2CO（001） planes. The adsorption of AlCl on the Al4CO4（001）and Al2CO（001） planes is stronger than that on the Al4C3（001） plane. The interaction strength of AlCl3, as well as AlCl2, with Al4CO4,Al2CO and Al4C3 is in the sequence of Al4CO4Al2CO〉Al4C3.
