An Electromotive Force Study of Lower Oxidation States of Lead, Cadmium, and Tin in Molten NaAlCl<sub>4</sub>

Munday, Theodore; Corbett, John D.

doi:10.1021/ic50041a042

Cited by 27 publications

(17 citation statements)

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“…The kinetics of depassivation and repassivation is incorporated in the mechanisms of passivity and stress corrosion cracking as has been reviewed by several authors (1,2). Burstein and Ashley (3) investigated the depassivation of a scratched iron disk electrode while rotating in buffer solutions composed primarily of KOH, H2B4OT, NaC104, and HC104.…”

Section: Resultsmentioning

confidence: 99%

“…Nernst plots were constructed using Co/Cr values obtained from the potential difference spectra using the following equation (21) Co/Cr = Ao/(Aoi-Ao) = (Ari-Ar)/Ar [1] where Ax (x = r or o) is the absorbance of species x at any given potential and Axi is the absorbance of species x at a potential where it is the only form of the redox couple present.…”

Section: Methodsmentioning

confidence: 99%

“…[2]) is rapid and the complexed radical anion QA'-is reduced at potentials consistent with Q reduction (Eq. [1]), hence only one cathodic wave corresponding to an overall two-electron reduction is observed. At very fast scan rates, reaction [2] may be "outrun" and two waves corresponding to stepwise one-electron reductions of Q to Q2-are observed.…”

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confidence: 99%

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Infrared Spectroscopic and Spectroelectrochemical Investigation of Chloranil in Molten Sodium Chloroaluminates

Flowers

Mamantov

1989

J. Electrochem. Soc.

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The infrared spectroscopic and spectroelectrochemical properties of tetrachloro-p-benzoquinone (chloranil or Q) in molten aluminum chloride-sodium chloride mixtures have been examined. Spectroscopic results suggest that in acidic melts [>50 mole percent (m/o) A1C13] chloranil exists as a Lewis acid adduct with A1C13 (or A12C17 ) coordinated at one of the carbonyl oxygens and at the carbon-carbon double bonds. No evidence for adduct formation was observed in basic melts (<50 m/o A1C13). Spectroelectrochemical data indicate that chloranil is reduced in an overall two-electron process in basic melts, in agreement with previously reported electrochemical results. In acidic melts, however, the data suggest stepwise one-electron reductions to produce the radical anion and dianion. The presence of two closely spaced one-electron reduction steps is confirmed by differential pulse voltammetry.

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

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Infrared Spectroscopic and Spectroelectrochemical Investigation of Chloranil in Molten Sodium Chloroaluminates

Flowers

Mamantov

1989

J. Electrochem. Soc.

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“…The second method involves the calculation of the standard potentials EB ~ and EA ~ corresponding to the respective reactions AICI4-+ 3e ~:e A1 + 4C1- [5] and 4A12C17-+ 3e ~ A1 + 7AlC14- [6] The equivalence point molar composition is adjusted for a minimum standard deviation on EB ~ and EA~ the equilibrium constant is then simply calculated from 4RT EB ~ -.~ EA ~ ~-' In KI [7] 3F A more detailed description of the procedure is given in Appendix B 9…”

Section: Resultsmentioning

confidence: 99%

“…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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Homopolyatomic Ions of the Post‐Transition Elements—Synthesis, Structure, and Bonding

Corbett¹

1976

Progress in Inorganic Chemistry

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An Electromotive Force Study of Lower Oxidation States of Lead, Cadmium, and Tin in Molten NaAlCl₄

Cited by 27 publications

References 0 publications

Infrared Spectroscopic and Spectroelectrochemical Investigation of Chloranil in Molten Sodium Chloroaluminates

Infrared Spectroscopic and Spectroelectrochemical Investigation of Chloranil in Molten Sodium Chloroaluminates

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

Homopolyatomic Ions of the Post‐Transition Elements—Synthesis, Structure, and Bonding

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An Electromotive Force Study of Lower Oxidation States of Lead, Cadmium, and Tin in Molten NaAlCl4

Cited by 27 publications

References 0 publications

Infrared Spectroscopic and Spectroelectrochemical Investigation of Chloranil in Molten Sodium Chloroaluminates

Infrared Spectroscopic and Spectroelectrochemical Investigation of Chloranil in Molten Sodium Chloroaluminates

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

Homopolyatomic Ions of the Post‐Transition Elements—Synthesis, Structure, and Bonding

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An Electromotive Force Study of Lower Oxidation States of Lead, Cadmium, and Tin in Molten NaAlCl₄