Properties of Electrolytic Solutions. XII. The Influence of Temperature on the Conductance of Electrolytes in Anisole<sup>1</sup>

Bien, G. S.; Kraus, Charles A.; Fuoss, Raymond M.

doi:10.1021/ja01324a011

Cited by 30 publications

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“…and a knowledge of the ratio of AO/AO, permits evaluation of the triple-ion dissociation constant, k. Various assumptions and estimates of this ratio ranging from 0.33 to 0.82 have been used (5,7,15). The results of the plot by the method of least squares of both eqs.…”

Section: Resultsmentioning

confidence: 99%

The Trifluoroacetic Acid Solvent System. Part IV. Triple Ions

Harriss¹,

Milne²

1972

Can. J. Chem.

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Electrolytes studied in 100'j/, trifluoroacetic acid exhibit a minimum in equivalent conductivity with increasing solute concentration. This behavior is accounted for by the formation of triple-ions at higher concentrations. Triple-ion dissociation constants, k , have been evaluated and, in general, they show the opposite trend with changing ion size to that of the ion-pair dissociation constants; that is the triple-ions of smaller ions are more dissociated. The experimentally observed trend is accounted for by using a partial ionic charge instead of unit charge for the ion-pair charges in the theoretical Fuoss expression for k .The excellent extrapolation of the triple-ion data to give a value of A°Kd for the ion-pair, which agrees well with that determined from a Fuoss plot, permits an estimate of A0 for LiO,CCF, from the triple-ion data.Les electrolytes etudies dans I'acide trifluoroacetique a 100% montrent un minimum, i conductivite tquivalente, pour une concentration croissante en solute. Ce phtnomine s'explique par la formation d'ions triples en concentrations elevees. Les constantes de dissociation des ions triples k ont ete evaluees; elles varient generalement en sens contraire, par rapport aux constantes de dissociation des paires d'ions, avec le changement dans la taille de l'ion. Cette tendance, observee experimentalement, a ete interpretee en utilisant une charge ionique partielle, au lieu de l'unite pour les charges des paires d'ions dans I'expression thtorique de Fuoss pour k.L'excellente extrapolation des donntes sur I'ion triple pour la valeur A°Kd de la paire d'ion, en bon accord avec la valeur tiree de la courbe de Fuoss, permet une estimation de A0 pour LiO,CCF, a partir des donnees sur I'ion triple.

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Section: Resultsmentioning

confidence: 99%

The Trifluoroacetic Acid Solvent System. Part IV. Triple Ions

Harriss¹,

Milne²

1972

Can. J. Chem.

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“…It is a solvent for electrolytes like tetraalkylammonium salts, which, owing to the low dielectric constant [4.3 at 298 K], exhibit weak dissociation into the cation and anion and even tend to form association complexes with the free ions. 23 For the study of these equilibria, conductivity measurements as a function of concentration and temperature were found most useful, as is shown in ref 23 where molar conductivities Λ are reported for tetrabutylammonium nitrate and tetrabutylammonium picrate. In Figure 9 we have plotted Λ 1/2 versus temperature T taking four series from these data.…”

Section: Arrest Of Nonaqueous Fluidsmentioning

confidence: 99%

“…An interesting case is the organic solvent anisole (methoxybenzene), with its normal melting point of 236 K and normal boiling point of 427 K being liquid in a wide temperature range. It is a solvent for electrolytes like tetraalkylammonium salts, which, owing to the low dielectric constant [4.3 at 298 K], exhibit weak dissociation into the cation and anion and even tend to form association complexes with the free ions . For the study of these equilibria, conductivity measurements as a function of concentration and temperature were found most useful, as is shown in ref where molar conductivities Λ are reported for tetrabutylammonium nitrate and tetrabutylammonium picrate.…”

Section: Arrest Of Nonaqueous Fluidsmentioning

confidence: 99%

“…The involved analysis in ref yields the limiting molar conductivity Λ 0 of the tetrabutylammonium [TBA] salts and the equilibrium constant K d of their dissociation into the TBA cation and the nitrate or picrate anions as a function of temperature. As shown in Figure , both quantities extrapolate to T 0 = 200–210 K. So, the arrest applies to both a dynamic and an equilibrium property.…”

Section: Arrest Of Nonaqueous Fluidsmentioning

confidence: 99%

“…Figure 10. Limiting molar conductivity and dissociation constant of tetrabutylammonium phosphate [TBAP] and nitrate [TBAN]complexes dissolved in anisole as a function of temperature 23. …”

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Arrest as a General Property of the Supercooled Liquid State

Sluyters

Sluyters‐Rehbach

2016

J. Phys. Chem. B

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Owing to the universal presence of intermolecular interactions, it has to be expected that at some well-defined lower temperature a liquid loses its dynamic properties like fluidity and self-diffusion. As a sequel to two earlier papers on the discovery of such an arrest temperature T0 for supercooled water at 243 K, where also the coexisting vapor pressure was found to become zero, in this paper a further study is undertaken of the behavior of a selection of other liquids. At first, two simple equations of state (van der Waals and virial) are shown in principle to predict a zero vapor pressure at a finite temperature. The interaction parameters B (second virial coefficient) and μJT (Joule-Thomson coefficient) of the vapor are found to become virtually infinite at a temperature T0,B, with a value equal or close to the T0 derived from the liquid properties. Just as earlier found for water, the latter is obtained by extrapolation of several available dynamic and equilibrium data, which should produce an intersection with the temperature axis at the same T0 value. With the exception of molten salts and liquid pure metals, this condition appears to be fulfilled quite accurately. Thus, the temperature of arrest is a general phenomenon for supercooled liquids. As an illustration, it is shown how the PVT diagram of carbon dioxide can be extended into the supercooled temperature region. It is argued that T0 is the temperature below which the Boltzmann energy, kT, is lower than the minimal energy needed for a molecule to break the interactions with its surrounding molecules. We propose to name this minimal energy, kT0, the multimolecular potential of the liquid object. The relationship of the liquid multimolecular potential with the pair potential, ε, of the molecular species is established for various examples and appears to be a proportionality with ε ≈ 2kT0.

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