In this paper,we have investigated the formation of the third-phase in tertiary amine(N235)-PtCl62--HCl system and the microscopic phase structural evolution of platinum-loaded organic phases before and after the occu...In this paper,we have investigated the formation of the third-phase in tertiary amine(N235)-PtCl62--HCl system and the microscopic phase structural evolution of platinum-loaded organic phases before and after the occurrence of the third-phase.The third-phase is characterized by various spectroscopic techniques,and the small angle X-ray scattering(SAXS)experiments demonstrate the appearance of nano-aggregates,i.e.,water-in-oil reversed micelles,in the third phase.The experimental results indicate that(1)formation of the third phase is related to the aggregation behaviors of nano-reversed micelles in which a super-concentrated hydrochloric acid formed with the H+to H2O molar ratio being much higher than that of the conventional 37 wt%saturated hydrochloric acid.(2)The occurrence of the super-concentrated HCl results in a great amount of H+and Cl-ions enriched and confined within the nano-water pools of W/O reversed micelles in third phase.Therefore,the coordination behaviors of platinum complex ions in that super-concentrated hydrochloric acid are very different from their corresponding behaviors in bulk aqueous solutions.It is possible that H+ions participate in the formation of such complexes as HmPtCl6z+in the super-concentrated hydrochloric acid.(3)The relative contents of various HmPtCl6z+complexes are different corresponding to the H+ion concentrations in confined nanowater pools.The association ability of the acidified tertiary amine N235 molecules(R3NH+)with various HmPtCl6z+complexes plays an important role in affecting the platinum extraction behaviors.展开更多
基金Supported by the National Natural Science Foundation of China(Grant Nos.50404004,50673005)China Postdoctoral Science Foundation Funded Project(Grant Nos.20070410002,200801007)
文摘In this paper,we have investigated the formation of the third-phase in tertiary amine(N235)-PtCl62--HCl system and the microscopic phase structural evolution of platinum-loaded organic phases before and after the occurrence of the third-phase.The third-phase is characterized by various spectroscopic techniques,and the small angle X-ray scattering(SAXS)experiments demonstrate the appearance of nano-aggregates,i.e.,water-in-oil reversed micelles,in the third phase.The experimental results indicate that(1)formation of the third phase is related to the aggregation behaviors of nano-reversed micelles in which a super-concentrated hydrochloric acid formed with the H+to H2O molar ratio being much higher than that of the conventional 37 wt%saturated hydrochloric acid.(2)The occurrence of the super-concentrated HCl results in a great amount of H+and Cl-ions enriched and confined within the nano-water pools of W/O reversed micelles in third phase.Therefore,the coordination behaviors of platinum complex ions in that super-concentrated hydrochloric acid are very different from their corresponding behaviors in bulk aqueous solutions.It is possible that H+ions participate in the formation of such complexes as HmPtCl6z+in the super-concentrated hydrochloric acid.(3)The relative contents of various HmPtCl6z+complexes are different corresponding to the H+ion concentrations in confined nanowater pools.The association ability of the acidified tertiary amine N235 molecules(R3NH+)with various HmPtCl6z+complexes plays an important role in affecting the platinum extraction behaviors.
