Immiscibility Gap in the System: LiCl-KCl-AlCl<sub>3</sub>.

Moore, R. H.

doi:10.1021/je60017a002

Cited by 10 publications

(8 citation statements)

References 1 publication

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“…In this experimental condition, the influence of the phase transition of the AlCl 3 -LiCl-KCl melt upon the redox potential was not observed, since there was no inflection point in the relation between the equilibrium potential and the temperature. On the other hand, an immiscibility gap was observed in the AlCl 3 -LiCl-KCl system, which contained AlCl 3 higher than 10 mol% [13]. In such a case, it is feared that there is a turning point on temperature dependence of the electrode potential.…”

Section: Electrochemical Properties Of the Al 3+ |Al Electrodementioning

confidence: 99%

Electrochemical properties of the Ag+|Ag and other reference electrodes in the LiCl–KCl eutectic melts

Shirai

Nagai

Uehara

et al. 2008

Journal of Alloys and Compounds

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Section: Electrochemical Properties Of the Al 3+ |Al Electrodementioning

confidence: 99%

Electrochemical properties of the Ag+|Ag and other reference electrodes in the LiCl–KCl eutectic melts

Shirai

Nagai

Uehara

et al. 2008

Journal of Alloys and Compounds

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“…The isothermal boundaries of the miscibility gap in the system LiCI-KCI-LiAlC14-KAlC14 have been measured at several temperatures by Moore (22). In the present work only the intersection of the gap with the liquidus surface was calculated, so a direct comparison is difficult.…”

Section: Kci-kaici (Fig 6)mentioning

confidence: 93%

Selection of ternary fused chlorides for the electrowinning of aluminum based on calculated thermodynamic properties

Pelton¹,

Skeaff²,

Bal³

et al. 1982

Can. J. Chem.

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. Can. J. Chem. 60, 1664 (1982). Phase diagrams and total vapour pressures in the reciprocal ternary systems LiCI-NaCI-LiAIC1,-NaAICl,, LiC1-KCILiAIC1,-KAICI,, and NaCI-KCI-NaAlC1,-KAICI, have been calculated by means of computerized optimization and interpolation techniques based on an analysis of the constituent binary systems.The system LiC1-NaCI-LiAlC1,-NaAlCl, exhibits an extensive composition region of one-phase liquid solution whereas the LiCI-KCI-LiAIC1,-KAICI, system has a miscibility gap which covers 50% of the composition region. Comparison of the calculated phase diagram with measured data for NaCI-KCI-NaAIC1,-KAICI, was made and the agreement between the two was found to be satisfactory.Temperatures and compositions of chloride electrolytes suitable for the electrowinning of aluminum have been proposed from the isothermal sections of the phase diagrams and total vapourpressure curves. In all of the systems, the total vapour pressure is greater than the minimum for non-volatilization.

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“…Previous literature on the LiCl/KCl/AlCl 3 ternary phase diagram shows similar phase separations when there is an excess of LiCl and KCl relative to AlCl 3 . 33 It was suggested that the small size of the Li + cations relative to [AlCl 4 ] − anions drives the system to preferentially phase separate into a KAlCl 4 phase and a LiCl/ KCl phase, rather than form a homogeneous solution. 33 Similarly here, Li + is much smaller than the tetrahalogallate species, and thus, a similar driving force exists for phase separation.…”

Section: Dispersion Of Colloidal Nanocrystals In Galliummentioning

confidence: 99%

Synthesis of Ternary and Quaternary Group III-Arsenide Colloidal Quantum Dots via High-Temperature Cation Exchange in Molten Salts: The Importance of Molten Salt Speciation

Ondry,

Gupta,

Zhou

et al. 2023

ACS Nano

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Colloidal semiconductor nanocrystals are an important class of materials which have many desirable optoelectronic properties. In their bulk phases, gallium-and aluminum-containing III−V materials such as GaAs, GaP, and Al 1−x Ga x As represent some of the most technologically important semiconductors. However, their colloidal synthesis by traditional methods is difficult due to the high temperatures needed to crystallize these highly covalent materials and the extreme reactivity of Ga-and Al-precursors toward organic solvents at such high temperatures. A recently developed paradigm shift in the synthesis of these materials is to use molten inorganic salts as solvents to prepare Ga-containing III− V colloidal nanocrystals by cation exchange of the corresponding indium pnictide (InPn) colloidal nanocrystals. There have been several successful applications of molten salt solvents to prepare III-phosphide colloidal nanocrystals. However, little is known about the nature of these reaction environments at the relevant reaction conditions and synthesis of III-arsenide colloidal nanocrystals remains challenging. Herein we report a detailed study on cation exchange of InPn nanocrystals using nominally Lewis basic molten salt solvents with added gallium halides. Surprisingly, these salt systems phase separate into two immiscible phases, and the nanocrystals preferentially segregate to one of the phases. Using a suite of in situ spectroscopy tools, we identify the phase the nanocrystals segregate to as Lewis neutral alkali tetrahalogallate molten salts. We apply in situ high-temperature Raman spectroscopy to identify the chemical species present in several molten salt compositions at experimentally relevant reaction conditions to elucidate a molecular basis for the reactivity observed. We then employ Lewis neutral KGaI 4 molten salts to prepare high-quality In 1−x Ga x As and In 1−x Ga x P nanocrystals and demonstrate that deviation from Lewis neutral conditions accelerate nanocrystal decomposition in the case of III-arsenide materials. Further, we expand to KAlI 4 -based molten salts to prepare In 1−x−y Ga x Al y As nanocrystals which represent an example of solution-synthesized quaternary III−V nanocrystals. These insights provide a molecular basis for the rational development of molten salt solvents, thus allowing the preparation of a diverse array of multicomponent III−V colloidal nanocrystals.

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Immiscibility Gap in the System: LiCl-KCl-AlCl₃.

Cited by 10 publications

References 1 publication

Electrochemical properties of the Ag+|Ag and other reference electrodes in the LiCl–KCl eutectic melts

Electrochemical properties of the Ag+|Ag and other reference electrodes in the LiCl–KCl eutectic melts

Selection of ternary fused chlorides for the electrowinning of aluminum based on calculated thermodynamic properties

Synthesis of Ternary and Quaternary Group III-Arsenide Colloidal Quantum Dots via High-Temperature Cation Exchange in Molten Salts: The Importance of Molten Salt Speciation

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Immiscibility Gap in the System: LiCl-KCl-AlCl3.

Cited by 10 publications

References 1 publication

Electrochemical properties of the Ag+|Ag and other reference electrodes in the LiCl–KCl eutectic melts

Electrochemical properties of the Ag+|Ag and other reference electrodes in the LiCl–KCl eutectic melts

Selection of ternary fused chlorides for the electrowinning of aluminum based on calculated thermodynamic properties

Synthesis of Ternary and Quaternary Group III-Arsenide Colloidal Quantum Dots via High-Temperature Cation Exchange in Molten Salts: The Importance of Molten Salt Speciation

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Immiscibility Gap in the System: LiCl-KCl-AlCl₃.