Chloroaluminate Equilibria in AlCl[sub 3]-NaCl Melts

Fannin, Armand A.; King, Lowell A.; Seegmiller, David W.

doi:10.1149/1.2404344

Cited by 61 publications

(38 citation statements)

References 12 publications

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“…The existence of AlCl À 4 and Al 2 Cl À 7 species in (KCl + AlCl 3 ) melts was evidenced in particular by Raman spectroscopy [14,15]. The existence of an Al 3 Cl À 10 species in AlCl 3 -rich melts was even postulated [16]. The Modified Quasichemical Model does not explicitly introduce complex anions.…”

Section: Introductionmentioning

confidence: 99%

Thermodynamic evaluation and optimization of the (NaCl+KCl+AlCl3) system

Robelin

Chartrand

Pelton

2004

The Journal of Chemical Thermodynamics

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Section: Introductionmentioning

confidence: 99%

Thermodynamic evaluation and optimization of the (NaCl+KCl+AlCl3) system

Robelin

Chartrand

Pelton

2004

The Journal of Chemical Thermodynamics

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“…By using successive potential differences between an acidic and a basic point, the cell voltage can be written as follows As previously discussed (32), the activity coefficients of A12C17-, CI-, and A1C14-are not known. However, as the concentrations of C1-in the basic region and A12C17-in the acidic side do not vary to a great extent, it can be assumed that the corresponding (TC1--)B and (TAI2C17--)A are constant (32).…”

Section: Resultsmentioning

confidence: 99%

“…3. Knowing nr the program computes K1 from every successive basic and acidic point and relation [4], then the equivalence point potential and the whole theoretical curve. From a similar development and the Nernst equation applied to reaction [5], the (EB ~ + EB J) can also be evaluated for each point in basic melts The final values of nQ, EA ~ --I-EA J, and EB ~ + EB J are obtained by successive modification of n~ in order that the standard deviation (~) is minimum.…”

Section: Appendixmentioning

confidence: 99%

On the Tetrachloroaluminate Dissociation in Aluminum Chloride‐1‐n Butylpyridinium Chloride Mixtures

Schoebrechts

Gilbert

1981

J. Electrochem. Soc.

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The dissociation of tetrachloroaluminate anions in room temperature AICI~-I-n butylpyridinium chloride mixtures has been investigated as far as both reproducibility and reliability are concerned. The determination of the dissociation constants is based on the aluminum electrode potential variation measured around the equimolar composition. Experimental conditions have been determined which avoid the reduction of the pyridinium cation by A1 in slightly basic melts and where the potentials of the A1 electrode are stable. The average values of the dissociation constants are, respectively, (1.2 _ 0.2)10 -1~, (4.5 • 0.4)10 -13, and (7.5 • 0.8)10 -13 at 40 ~ 49 ~ and 55~ and are systematically lower than previously published values. The corresponding average values of hH and AS are, respectively, equal to 20.3 kcal mo1-1 and 6.5 eu. It has also been shown that the dissociation equilibrium of A1C14-into A12C17-and C1-is the only one required even in very acidic melts (up to 66.6 m/o of A1CI~), provided a correction is made for the junction potential.For the past few years, several groups of scientists have been interested in aluminum chloride containing melts. Most of these investigations deal with A1C18-alkali halide mixtures because of their particular properties. In particular, the chloroacidity (pC1) can be varied to a large extent, especially about the equimolar composition range (1-4). It has also been shown that the acidic nature of such melts stabilizes low oxidation state ions and organic radical cations (5-12). However, as pointed out by Koch et al., the use of aluminum chloride-inorganic chloride molten salts for organic reaction investigation is limited, essentially because of temperature problems (13).Recently, a new molten salt, first reported by Hurley and Wier (14), namely a 67/33 mol percent (m/o) aluminum chloride-ethylpyridinium bromide mixture, has been proposed as solvent for organic studies (15). It is liquid at room temperature, apparently very acidic (in a chloroacidity sense), and exhibits a large electrochemical window. However, although it has been used successfully to investigate different organic or inorganic systems (13,15,16), no quantitative data exist, either about the acidic strength of such melt or about the dependence of the acidic properties with respect to the melt composition. The main reason is that the mixture ethylpyridinium bromide-A1C13 is liquid at room temperature only in a limited range of composition, close to 2:1 and no investigation has been made outside this range.As a consequence, investigations have been directed to mixtures of A1C18 with other pyridinium salts, mainly n-methyl and n-butylpyridinium chlorides. The latter appears to be the most interesting; it is liquid at temperatures lower than 40~ across a large composition range (66-43 m/o of A1C13) whereas the former mixture is liquid at room temperature only in the range of 2:1 composition. Physical and spectroscopic properties of these melts (pure or mixed with benzene) have been investigated by Osteryoung et al...

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“…Based on the hypothesis, the relation between current and time was deduced in the document [30]. The nucleation model was as follows:…”

Section: Chronoamperometrymentioning

confidence: 99%

The electrochemical behavior of Dy(III) in eutectic LiF-DyF3 at W electrode

Yang

Wang

et al. 2016

Ionics

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The electrochemical reduction process of Dy ion on tungsten electrode at 1103 K in Dy 2 O 3 -LiF-DyF 3 molten system was studied by cyclic voltammetry, chronoamperometry, and chronopotentiometry methods with a three-electrode system on the electrochemical workstation AUTOLAB. The results showed that Dy 3+ could be deposited at around −0.75 Von inert W electrode compared with platinum electrode. The reduction process of Dy ion on W electrode occurred in a single step with the exchange of three electrons because one reduction peak was observed, and the calculated transfer electron number was three. Chronoamperograms indicated that the nucleation process of dysprosium ions was instantaneous three-dimensional nucleation on a tungsten electrode. The cathode electrochemical process on the tungsten electrode was controlled by the diffusion of ions, and the diffusion coefficient was 1.159 × 10 −4 cm 2 /s, which was calculated from a chronopotentiogram.

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Chloroaluminate Equilibria in AlCl[sub 3]-NaCl Melts

Cited by 61 publications

References 12 publications

Thermodynamic evaluation and optimization of the (NaCl+KCl+AlCl3) system

Thermodynamic evaluation and optimization of the (NaCl+KCl+AlCl3) system

On the Tetrachloroaluminate Dissociation in Aluminum Chloride‐1‐n Butylpyridinium Chloride Mixtures

The electrochemical behavior of Dy(III) in eutectic LiF-DyF3 at W electrode

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