The transfer of anions at the aqueus/organic solutions interface studied by current-scan polarography with the electrolyte dropping electrode

Kihara, Sorin; Suzuki, Mitsuko; Maeda, Kohji; Ogura, Kaoru; Matsui, Masanao

doi:10.1016/0022-0728(86)90320-7

Cited by 63 publications

(30 citation statements)

References 18 publications

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“…Most probably this is due to the rather short perturbation caused by this technique. Unlike in previous studies with the dropping electrolyte electrode (four-electrode technique) 23 we could obtain reliable data for the ions ClO 1 It is interesting to stress that although the radii in the series of Cl À , Br À , and I À increase in the order as written, the radii of XO 3 À decrease in the same direction. It is worth noting here that although several attempts have been made for modifying the simple electrostatic Born theory, e.g.…”

contrasting

confidence: 59%

Standard Gibbs energies of transfer of halogenate and pseudohalogenate ions, halogen substituted acetates, and cycloalkyl carboxylate anions at the water|nitrobenzene interface

Gulaboski

Riedl

Scholz

2003

Phys. Chem. Chem. Phys.

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The previously introduced three-phase electrode technique was used to determine the Gibbs energies of transfer of ClO 3 Cl,Br,I), and cycloalkyl carboxylate anions ((CH 2 ) n COO À , n ¼ 3,. . .,7) at the water|nitrobenzene interface. Whereas the data for the small inorganic ions can easily be understood in terms of ion-dipole interactions, the data of the organic ions need consideration of charge delocalisation and its effect on the enthalpy and entropy of solvation.

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contrasting

confidence: 59%

Standard Gibbs energies of transfer of halogenate and pseudohalogenate ions, halogen substituted acetates, and cycloalkyl carboxylate anions at the water|nitrobenzene interface

Gulaboski

Riedl

Scholz

2003

Phys. Chem. Chem. Phys.

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“…13. In most cases, our calculated values are more negative than those observed [43][44][45][46][47][48]. We have no explanation as to why log P values obtained from solubility measurements, from direct partition experiments, and from the variation of pKa with solvent yield reasonably self-consistent values, and yet log P values obtained from electrochemical methods do not appear to agree with the first set.…”

Section: Resultscontrasting

confidence: 54%

“…Details of all the log P values for ions and ionic species are in Table 5 In addition to log P values for ions obtained from solubility or distribution experiments, there are a number of log P values from electrochemical experiments [43][44][45][46][47][48]. Unfortunately, there is no consistency between the two sets of log P values.…”

Section: Resultsmentioning

confidence: 99%

The transfer of neutral molecules, ions and ionic species from water to benzonitrile; comparison with nitrobenzene

Abraham

Acree

2011

Thermochimica Acta

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Equations have been constructed for the transfer of 64 neutral solutes from water and from the gas phase to the solvent benzonitrile. The equations contain five descriptors and can be used to predict further values of the water-benzonitrile and gas-benzonitrile partition coefficients for a wide range of solutes. The water-benzonitrile equation has been extended to include ions and ionic species derived from acids by loss of a proton and bases by acceptance of a proton. Only two further descriptors are needed, one for anions and one for cations. A previous equation for transfer of neutral solutes from water to nitrobenzene has also been extended to include ions and ionic species. Comparison of the equations for transfer to benzonitrile and to nitrobenzene shows that the two solvents behave quite similarly, although benzonitrile as a solvent is a stronger hydrogen bond base.

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“…Here, l lc is the limiting current, I the instantaneous current. Hence, the transfer is concluded to be polarographically reversible similarly to the transfers of most of univalent ions from W to Org investigated previously [2,3,6,11 ].…”

Section: Supporting Electrolytes In Fa and Nxmentioning

confidence: 73%

The Ion Transfer From Aqueous(w), Formamide(fa) or W-Fa Mixtures to Organic Solution Studied by Polarography at the Electrolyte Solution Dropping Electrode

et al. 1991

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Formamide or aqueous-formamide mixture is introduced for the ion transfer voltammetry at a liquid/liquid interface as one phase in place of the aqueous phase. The transfer of I-, BF4-, C104-and CH3(CH2)~(CH3)3N+ (n>_1) was investigated at the interface of aqueous, formamide or the aqueousformamide mixtures and 2-nitro-m-xylene.The transfer of these ions was confirmed to be polarographically reversible. The relations are discussed between the standard Gibbs transfer free energy, L\G°~•, of these ions and the nature of the transferring ions or the properties of solvents based on the halfwave potentials in the polarograms. The AG°a of small anions from formamide to nitroxylene are smaller than those from aqueous. The effect of the addition of CH2 in CH3(CH2)n(CH3)3N+ on AG°~ from formamide to nitroxylene is smaller than that from aqueous.Key words formamide, aqueous-formamide mixture, ion transfer polarography at a liquid/liquid interface Formamide (FA) is a liquid at ordinary temperature in spite of its small molecular weight and has a large dielectric constant (e), dipole moment (it), donor number (DN) and acceptor number (AN). Since FA is a good solvent for inorganic salts, a structured solvent through hydrogen bonding and immiscible with some organic solvents of low [1], FA has been considered to be a solvent which resembles closely to water (W). In detail, however, considerable differences exist between properties of FA and W, which may reflect on the solute-solvent interaction of an ion in the solvents. If we use FA or W-FA as solvents instead of W taking into account the differences, new fields will be developed for the recognition of ions or molecules.In the present paper, the applicability of the ion transfer voltammetry [2] at the interface between FA or W-FA mixture and organic solution (Org) is demonstrated, and the ion-solvent interactions in W, FA and W-FA mixture are discussed based on the results obtained by the ion transfer polarography. EXPERIMENTAL Polarographic measurementThe polarographic cell, potentiostat, galvanostat, function generator, X-Y recorder, and the apparatus for JR drop compensation employed in the present work were identical to those described in the previous paper on the ion transfer at the W/ Org interface [3]. In recording the polarograms, W, FA or W-FA mixture containing 0.1 M Li2SO4 as the supporting electrolyte (SE) was forced upward or downward dropwise into Org containing various salts as SE through a capillary made of Teflon fluororesin. The objective ion was added into W, FA, or W-FA mixture. The mean flow rate of W, FA or W-FA mixture were 0.02 -0.05 ml s-l, and the drop-time were 3 -6 s, at open circuit. Current-scan polarograms were recorded scanning the applied current at a rate of 0.5 µA s-1 with the aid of two silver/silver chloride electrodes, SSE, and measuring the potential difference, AV, between W, FA or W-FA mixture and Org using SSE and a tetraphenylborate, TPhB-, ion selective electrode, TPhBE [3]. Here, w containing 1 M LiCI was used as the electr...

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The transfer of anions at the aqueus/organic solutions interface studied by current-scan polarography with the electrolyte dropping electrode

Cited by 63 publications

References 18 publications

Standard Gibbs energies of transfer of halogenate and pseudohalogenate ions, halogen substituted acetates, and cycloalkyl carboxylate anions at the water|nitrobenzene interface

Standard Gibbs energies of transfer of halogenate and pseudohalogenate ions, halogen substituted acetates, and cycloalkyl carboxylate anions at the water|nitrobenzene interface

The transfer of neutral molecules, ions and ionic species from water to benzonitrile; comparison with nitrobenzene

The Ion Transfer From Aqueous(w), Formamide(fa) or W-Fa Mixtures to Organic Solution Studied by Polarography at the Electrolyte Solution Dropping Electrode

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