The saturation vapour pressure and decomposition potential of ThCl4 solutions in molten alkali chlorides

Smirnov, M.V.; Kudyakov, V. Ya.

doi:10.1016/0013-4686(84)80040-7

Cited by 8 publications

(5 citation statements)

References 2 publications

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“…In this respect it is interesting that vapor pressure measurements over molten ThCl 4 -ACl mixtures show that the predominant vapor species are ThCl 4 (g), ACl(g) and complexes with the general stoichiometry AThCl 5 (g). 14 Such a behavior supports the stabilization of the 50 : 50 mixture with associated thorium chloride species. Further increase of the ThCl 4 mol fraction may extend the linkage to form a three edge-sharing octahedral species Th 3 Cl 14 2Ϫ (Fig.…”

Section: Associated Octahedral Thorium Chloride Ions At Composition X...mentioning

confidence: 60%

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Co-ordination of thorium(IV) in molten alkali-metal chlorides and the structure of liquid and glassy thorium(IV) chloride

Photiadis¹,

Papatheodorou²

1999

J. Chem. Soc., Dalton Trans.

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Raman spectra of molten ThCl 4 -ACl (A = Li, Na, K or Cs) mixtures have been measured. The complete composition range has been studied for all systems at temperatures up to 960 ЊC. The spectral changes upon melting the binary compounds A 2 ThCl 6 , A 3 ThCl 7 and the pure crystalline ThCl 4 were also measured. The data indicate that in molten mixtures rich in alkali-metal chloride the predominant species are the ThCl 6 2Ϫ octahedra [ν 1 (A 1g ) 297 and ν 5 (F 2g ) 125 cm Ϫ1 ] in equilibrium with the ThCl 7 3Ϫ pentagonal bipyramid. With increasing ThCl 4 mole fraction above 0.3 the frequency of the ν 1 (A 1g ) band increases continuously reaching its maximum (≈340 cm Ϫ1 ) in pure molten ThCl 4 . It appears that in mixtures rich in ThCl 4 edge bridging of thorium() octahedra occurs yielding chain species of the type [Th n Cl 4n ϩ 2 ] 2Ϫ and [Th n Cl 4n Ϫ 2 ] 2ϩ where the end Th atoms of the chain are six-and four-fold co-ordinated for the anion and cation respectively. The known ionic character of these melts suggests that the chain length is rather small and that most probably the species have low n values (e.g. Th 2 Cl 10 2Ϫ , Th 3 Cl 14 2Ϫ, Th 3 Cl 10 2ϩ , . . .). Glassy ThCl 4 was formed by slow cooling of the melt. The vibrational modes and the inferred structure of the glass are similar to those of the melt.

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Section: Associated Octahedral Thorium Chloride Ions At Composition X...mentioning

confidence: 60%

“…This behavior was attributed to the formation of ThCl 6 2Ϫ complex ions in these melts. Vapor pressure measurements 14 over the ThCl 4 -ACl molten mixtures show negative deviations from Raoult's law indicative of growing complexation of the thorium ions in these melts which increases in the sequence from LiCl to CsCl.…”

Section: Introductionmentioning

confidence: 95%

Co-ordination of thorium(IV) in molten alkali-metal chlorides and the structure of liquid and glassy thorium(IV) chloride

Photiadis¹,

Papatheodorou²

1999

J. Chem. Soc., Dalton Trans.

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“…Conditions have been evaluated for an operating temperature of the splash 'condenser' of say 775uC to achieve a target elimination of thorium chloride in the gas phase down to a level such that ,5 ppm Th contaminates the 'TiO 2 ' equivalent product. Using experimental data reported by Smirnov and Kudyakov, 27 it can be shown to achieve this objective requires stabilisation of the dissolved ThCl 4 in the binary potassium chloride melt at y0 . 5 mol-%.…”

Section: Discussionmentioning

confidence: 99%

Co-production of steel and titanium: process engineering feasibility

Warner¹

2007

Mineral Processing and Extractive Metallurgy

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Continuous smelting of ilmenite is proposed, eliminating chlorine based technology except perhaps as a means for dealing with associated radioactivity. Concentrates are fed onto the first of three melt circulation loops, in which optionally both the oxidic melt and the liquid steel layers may be circulated. Molten iron formed joins the circulating bottom layer of liquid steel, which extracts impurities including chromium, silicon, manganese, vanadium, niobium, aluminium and phosphorus. Liquid steel is withdrawn for refining before continuous casting. The oxidic melt has its carbide content increased in the second of the melt circulation loops. Continuous vacuum refining is then conducted in the third loop operating at 1 mbar using vacuum steel degassing steam jet ejector systems, yielding a theoretical (TiO 2 zZrO 2 ) equivalent in the titanium oxycarbide melt of 'four nines' (99 . 99%) purity at 84% recovery. The refined melt feeds the electrochemical deoxygenation reactor described in the patent literature for continuous production of liquid titanium.

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“…We adopted one type of machine learning potentials, the Gaussian approximation potential (GAP), to investigate the binary systems of molten thorium tetrachloride (ThCl 4 )–sodium chloride (NaCl) and uranium trichloride (UCl 3 )–NaCl. ThCl 4 and UCl 3 are common fuel nuclear materials, and in practice, they are usually found mixed with other metal halides. − The binary ThCl 4 –NaCl and UCl 3 –NaCl subsystems could be regarded as a simplified model fuel system for future molten chloride-based 232 Th– 233 U breeder reactors such as the molten chloride fast reactor (MCFR). The system ThCl 4 –NaCl shows a wide An solubility range above 600 °C, which is caused by the presence of the congruent chloride phase Na 2 ThCl 6 sandwiched between two eutectics.…”

Section: Introductionmentioning

confidence: 99%

“…A fundamental understanding of the structure of these chloride systems with temperature will provide and enhance the understanding of their thermophysical properties relevant to liquid fueled MSR development. Although studies of ThCl 4 –NaCl and UCl 3 –NaCl mixtures have been reported, ,,− understanding the local structures and dynamics in these materials still remains elusive. Here, the composition with the actinide molar fraction of 0.273 (ThCl 4 –NaCl) and 0.286 (UCl 3 –NaCl), close to their eutectic compositions, is selected for our study.…”

Section: Introductionmentioning

confidence: 99%

Actinide Molten Salts: A Machine-Learning Potential Molecular Dynamics Study

Nguyen

Rousseau

Paviet

et al. 2021

ACS Appl. Mater. Interfaces

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Actinide molten salts represent a class of important materials in nuclear energy. Understanding them at a molecular level is critical for the proper and optimal design of relevant technological applications. Yet, owing to the complexity of electronic structure due to the 5f orbitals, computational studies of heavy elements in condensed phases using ab initio potentials to study the structure and dynamics of these elements embedded in molten salts are difficult. This lack of efficient computational protocols makes it difficult to obtain information on properties that require extensive statistical sampling like transport properties. To tackle this problem, we adopted a machine-learning approach to study ThCl 4 −NaCl and UCl 3 −NaCl binary systems. The machine-learning potential with the density functional theory accuracy allows us to obtain long molecular dynamics trajectories (ns) for large systems (10 3 atoms) at a considerably low computing cost, thereby efficiently gaining information about their bonding structures, thermodynamics, and dynamics at a range of temperatures. We observed a considerable change in the coordination environments of actinide elements and their characteristic coordination sphere lifetime. Our study also suggests that actinides in molten salts may not follow well-known entropyscaling laws.

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The saturation vapour pressure and decomposition potential of ThCl4 solutions in molten alkali chlorides

Cited by 8 publications

References 2 publications

Co-ordination of thorium(IV) in molten alkali-metal chlorides and the structure of liquid and glassy thorium(IV) chloride

Co-ordination of thorium(IV) in molten alkali-metal chlorides and the structure of liquid and glassy thorium(IV) chloride

Co-production of steel and titanium: process engineering feasibility

Actinide Molten Salts: A Machine-Learning Potential Molecular Dynamics Study

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