Properties of Electrolytic Solutions. III. The Dissociation Constant

Fuoss, Raymond M.; Kraus, Charles A.

doi:10.1021/ja01330a023

Cited by 237 publications

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“…5 The data are reproduced Fig. 3, and the fitting distance is 0.66 nm, which is a realistic value for this distance, as the sum of radii is equal to 0.60-0.72 nm depending on the radius chosen.…”

Section: A Case Imentioning

confidence: 81%

Application of classical thermodynamics to the conductivity in non-polar media

Gourdin-Bertin

Chassagne

2016

The Journal of Chemical Physics

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Articles you may be interested inElectrical conductivity in non-polar media is a subject which recently regained interest. If most of experiments and theoretical developments were done more than 50 years ago, new experiments and theories have been recently published. As the electrical conductivity describes, at low field, the equilibrium state of a system, it is natural to apply theories based on equilibrium thermodynamics. In this article, well-established classical thermodynamics and solvations models are applied to recently published data. This enables to get a new insight in intriguing phenomena, such as the linear dependence of the conductivity on the concentration of ionic surfactant and the evaluation of conductivity for the mixture of two miscible fluids, such as alcohol and alcane, which have very different conductivities. Published by AIP Publishing. [http://dx

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Section: A Case Imentioning

confidence: 81%

Application of classical thermodynamics to the conductivity in non-polar media

Gourdin-Bertin

Chassagne

2016

The Journal of Chemical Physics

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“…(1, 27) is negligible. As is true for the ion-pair QBr, discussed above, the dissociation constant of the ion-pair QHB in chloroform has not been measured but can be estimated to be about (1,19,20). Therefore, dissociation may or may not be significant at concentrations as high as M. However, a calibration curve of absorbance at 440 nm versus CQHBTo in chloroform was found to be linear with zero intercept over the range of concentrations of interest.…”

Section: ~A D S B T B ~~~( a ) -Imentioning

confidence: 94%

“…The ion-pair QBr is present at too low concentrations to dimerize in chloroform (1). Dissociation of QBr in chloroform has not been studied but, based on the behavior of similar compounds in solvents of various dielectric constants, its dissociation constant is expected to be about lop7 (19,20). Thus, in the concentration range studied the undissociated ion-air will red om in ate, but at the lower end of the range there could possibly be significant dissociation.…”

Section: Distribution Of Q B Rmentioning

confidence: 99%

Adsorption of tetrahexylammonium – bromothymol blue ion-pairs at the chloroform–water interface

Amankwa¹,

Cantwell²

1991

Can. J. Chem.

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LAWRENCE AMANKWA and FREDERICK F. CANTWELL. Can. J. Chem. 69, 88 (1991) Porous membrane phase separators are used to study the adsorption of the cation tetrahexylammonium (Qt), of the anion bromothymol blue (HB-) and of the ion-pair formed between them (QHB) at the liquid-liquid interface in a rapidly stirred mixture of chloroform and aqueous buffer. Adsorption isotherms in all three cases follow the Langmuir equation. The anion HBis much more strongly adsorbed than the ion-pair QHB. The porous membrane technique readily permits measurement of simultaneous adsorption of the two species HB-and QHB, and thereby allows a study of their competitive adsorption. When QHB is adsorbed in the presence of an excess of HB-both the saturated (monolayer) interfacial concentration of QHB and the logarithm of the adsorption equilibrium constant for QHB decrease linearly with an increase in interfacial concentration of HB-. This shows quantitatively that coadsorption of QHB and HB-involves a direct competition for space at the interface and also that the presence of adsorbed HB-changes the adsorbent properties of the interface. Analytical implications for solvent extraction are discussed. Solvent extraction of ion-pairs has been (1) and remains (2,3) an important technique for the analytical determination of ionic species. The equilibrium aspects of the distribution of ion-pairs between two bulk liquid phases have been extensively studied (1,4) and, more recently, the kinetic aspects of ion-pair extraction between bulk liquid phases have been investigated (5).Depending on the surface-activity of the sample ion, of the reagent ion and of the ion-pair formed between them, interfacial adsorption may play a major role in determining both the equilibrium and kinetic extraction behavior of ion-pairs. The use of porous membrane phase separators makes possible measurement of the amount of solute adsorbed at the liquidliquid interface in a vigorously stirred solvent extraction system and therefore permits the measurement of adsorption isotherms of solutes between the interface and the bulk liquid phases (6-9). Adsorption isotherms previously have been measured by this technique for interfacial adsorption of ion-pairs formed between cationic metal-ligand complexes and simple anions (10) and for the ion-pair tetrahexylammoniumpicrate (QP) (1 1). Because the technique allows measurement of concentrations in both liquid phases it makes possible the discrimination of two species simultaneously adsorbed at the interface. This is an advantage over conventional techniques for measuring interfacial adsorption such as those based on interfacial tension or pressure. This advantage is utilized in studying the tetrahexylammonium-bromothymol blue system. 'TO whom correspondence should be addressed.Bromothymol blue is one of the most often used anionic reagents for ion-pair extraction (I). In the present study bromothymol blue anion, HB-, which is surface-active, is used to form a surface-active ion pair, QHB, with tetrahexylammonium cation, Q + , w...

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“…For example, Fuoss and Kraus (15) observed that (i-amyl),Npicrate forms two liquid phases in benzene above a concentration of 0.1 M. Other examples are HFeC1, (16) and NH,FeCl, (17) in diethylether and similarly Ga2Cl, (17) and (Bu),NAlBu, (18) in benzene. In all of these cases the two phases occur only within a certain range referred to as the miscibility gap.…”

Section: Kineticsmentioning

confidence: 99%

The two liquid phase system NaAl(ethyl)4 – benzene–HMPA

Medley¹,

Ahmad²,

Day³

1985

Can. J. Chem.

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A detailed study of complexation of the sodium ion by HMPA2 has been made using the system[Formula: see text]where HMPA is observed to be a strong donor towards Na+ but does not complex AlEt4−. This system forms two liquid phases at low HMPA:Na+ molar ratios with the salt and the HMPA, up to a 4:1 HMPA:Na+ ratio, occurring only in the lower phase. Based on a variety of experimental techniques, reasonable proposals of the solute species in the lower phase as a function of HMPA:Na+ ratio are presented. A 2.5:1 ratio of HMPA:Na+ is observed to be particularly significant. This ratio is rationalized in terms of a bridging HMPA molecule resulting in a cationic species with the stoichiometry [2Na•5HMPA]2+. It is found that the 27Al and 1H nmr spectra are determined primarily by quadrupole relaxation of the 27Al nucleus rather than by exchange.

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Properties of Electrolytic Solutions. III. The Dissociation Constant

Cited by 237 publications

References 0 publications

Application of classical thermodynamics to the conductivity in non-polar media

Application of classical thermodynamics to the conductivity in non-polar media

Adsorption of tetrahexylammonium – bromothymol blue ion-pairs at the chloroform–water interface

The two liquid phase system NaAl(ethyl)4 – benzene–HMPA

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