The solvation of carbon dioxide in sea water plays an important role in the carbon circle and the world climate. The salting-out/salting-in mechanism of CO2 in electrolyte solutions still remains elusive at molecule l...The solvation of carbon dioxide in sea water plays an important role in the carbon circle and the world climate. The salting-out/salting-in mechanism of CO2 in electrolyte solutions still remains elusive at molecule level. The ability of ion salting-out/salting-in CO2 in electrolyte solution follows Hofmeister Series and the change of water mobility induced by salts can be predicted by the viscosity B-coefficients. In this work, the chemical potential of carbon dioxide and the dynamic properties of water in aqueous NaCl, KF and NaClO4 solutions are calculated and analyzed. According to the viscosity B-coefficients, NaClO4 （0.012） should salt out the carbon dioxide relative to in pure water, but the opposite effect is observed for it. Our simulation results suggest that the salting-in effect of NaClO4 is due to the strongly direct anion-CO2 interaction. The inconsistency between＂ Hofmeister Series and the viscosity B-coefficient suggests that it is not always right to indicate whether a salt belongs to salting-in or salting-out just from these properties of the salt solution in the absence of solute.展开更多
核级锆(Zr)和核级铪(Hf)是保障核工业发展的重要基础材料。溶剂萃取分离是制备核级锆铪的技术关键。本文从溶液化学平衡角度,阐释了酸性介质有利于抑制锆铪离子的水解聚合,提高其反应活度。根据软硬酸碱理论和活性功能基差异,总结了近...核级锆(Zr)和核级铪(Hf)是保障核工业发展的重要基础材料。溶剂萃取分离是制备核级锆铪的技术关键。本文从溶液化学平衡角度,阐释了酸性介质有利于抑制锆铪离子的水解聚合,提高其反应活度。根据软硬酸碱理论和活性功能基差异,总结了近年来研发的萃取剂主要有含O, N, P和S等不同类型,并评价了其主要优点和不足。结合有机膦酸类萃取剂的二聚体结构特征,阐述了具有电子给体特征的惰性有机溶剂对该类萃取剂的“解聚”作用机制。并且,从界面化学反应平衡角度,解释了具有一定溶解度的有机溶剂,对提升萃取反应效率的必要性。除此之外,还结合软硬酸碱理论和霍夫迈斯特序列,综述了锆铪溶剂萃取分离体系助萃剂、盐析剂和反萃剂等选用的基本原则,以期为锆铪高效溶剂萃取分离体系的研发和应用提供基础理论指导。展开更多
文摘The solvation of carbon dioxide in sea water plays an important role in the carbon circle and the world climate. The salting-out/salting-in mechanism of CO2 in electrolyte solutions still remains elusive at molecule level. The ability of ion salting-out/salting-in CO2 in electrolyte solution follows Hofmeister Series and the change of water mobility induced by salts can be predicted by the viscosity B-coefficients. In this work, the chemical potential of carbon dioxide and the dynamic properties of water in aqueous NaCl, KF and NaClO4 solutions are calculated and analyzed. According to the viscosity B-coefficients, NaClO4 （0.012） should salt out the carbon dioxide relative to in pure water, but the opposite effect is observed for it. Our simulation results suggest that the salting-in effect of NaClO4 is due to the strongly direct anion-CO2 interaction. The inconsistency between＂ Hofmeister Series and the viscosity B-coefficient suggests that it is not always right to indicate whether a salt belongs to salting-in or salting-out just from these properties of the salt solution in the absence of solute.
文摘核级锆(Zr)和核级铪(Hf)是保障核工业发展的重要基础材料。溶剂萃取分离是制备核级锆铪的技术关键。本文从溶液化学平衡角度,阐释了酸性介质有利于抑制锆铪离子的水解聚合,提高其反应活度。根据软硬酸碱理论和活性功能基差异,总结了近年来研发的萃取剂主要有含O, N, P和S等不同类型,并评价了其主要优点和不足。结合有机膦酸类萃取剂的二聚体结构特征,阐述了具有电子给体特征的惰性有机溶剂对该类萃取剂的“解聚”作用机制。并且,从界面化学反应平衡角度,解释了具有一定溶解度的有机溶剂,对提升萃取反应效率的必要性。除此之外,还结合软硬酸碱理论和霍夫迈斯特序列,综述了锆铪溶剂萃取分离体系助萃剂、盐析剂和反萃剂等选用的基本原则,以期为锆铪高效溶剂萃取分离体系的研发和应用提供基础理论指导。
