Insights into the structural dynamics, thermophysical properties, and thermodynamics of the NaCl-ThCl4 and NaCl-UCl4 systems

IF 5.2 2区 化学 Q2 CHEMISTRY, PHYSICAL
N.T.H. ter Veer , W.K. de Vries , C.T.C. Heyning , T.F. Abbink , J.A. Ocádiz-Flores , A.E. Gheribi , R.J.M. Konings , A.L. Smith
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引用次数: 0

Abstract

The structural, thermochemical, and thermophysical properties of the AnCl4, and NaCl-AnCl4 (An = Th, U) melts were investigated using molecular dynamics (MD) simulations based on the Polarisable Ion Model (PIM). New force fields were proposed and used to compute key properties including density, thermal expansion, enthalpy of mixing, heat capacity, as well as the local structure and chemical speciation in the molten (Na, An)Clx (An = Th, U) salts. Thermodynamic models were then developed based on the CALPHAD method, using both PIM-MD and experimental data as input. Employing the modified quasichemical formalism in the quadruplet approximation for the liquid solution, the models account for the chemical speciation in the melt as calculated by MD simulations, and reproduce well phase equilibria in those systems. In particular, the models included monomeric and dimeric species to represent the physical nature of the ionic melt, which shows progressive oligomerisation with increasing AnCl4 fraction. Our studies confirm that the melt becomes highly volatile at high AnCl4 fractions, which is discussed in light of the results obtained herein.
深入了解NaCl-ThCl4和NaCl-UCl4体系的结构动力学、热物理性质和热力学
采用基于极化离子模型(PIM)的分子动力学(MD)模拟研究了AnCl4和NaCl-AnCl4 (An = Th, U)熔体的结构、热化学和热物理性质。提出了新的力场,并用于计算熔融(Na, An)Clx (An = Th, U)盐的密度、热膨胀、混合焓、热容、局部结构和化学形态等关键性能。基于CALPHAD方法,以PIM-MD和实验数据为输入,建立了热力学模型。采用改进的准化学形式的四重态近似的液体溶液,模型解释了化学形态在熔体中计算的MD模拟,并再现了这些系统的相平衡。特别是,模型包括单体和二聚体,以代表离子熔体的物理性质,随着AnCl4分数的增加,离子熔体表现出逐渐的寡聚化。我们的研究证实,熔体在高AnCl4分数下变得高度挥发,这是根据本文得到的结果进行讨论的。
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来源期刊
Journal of Molecular Liquids
Journal of Molecular Liquids 化学-物理:原子、分子和化学物理
CiteScore
10.30
自引率
16.70%
发文量
2597
审稿时长
78 days
期刊介绍: The journal includes papers in the following areas: – Simple organic liquids and mixtures – Ionic liquids – Surfactant solutions (including micelles and vesicles) and liquid interfaces – Colloidal solutions and nanoparticles – Thermotropic and lyotropic liquid crystals – Ferrofluids – Water, aqueous solutions and other hydrogen-bonded liquids – Lubricants, polymer solutions and melts – Molten metals and salts – Phase transitions and critical phenomena in liquids and confined fluids – Self assembly in complex liquids.– Biomolecules in solution The emphasis is on the molecular (or microscopic) understanding of particular liquids or liquid systems, especially concerning structure, dynamics and intermolecular forces. The experimental techniques used may include: – Conventional spectroscopy (mid-IR and far-IR, Raman, NMR, etc.) – Non-linear optics and time resolved spectroscopy (psec, fsec, asec, ISRS, etc.) – Light scattering (Rayleigh, Brillouin, PCS, etc.) – Dielectric relaxation – X-ray and neutron scattering and diffraction. Experimental studies, computer simulations (MD or MC) and analytical theory will be considered for publication; papers just reporting experimental results that do not contribute to the understanding of the fundamentals of molecular and ionic liquids will not be accepted. Only papers of a non-routine nature and advancing the field will be considered for publication.
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