The transfer of carboxylate and sulphonate anions at the aqueous/organic solution interface studied by polarography with the electrolyte solution dropping electrode

Kihara, Sorin; Suzuki, Mitsuko; Sugiyama, Masahito; Matsui, Masanao

doi:10.1016/0022-0728(88)80352-8

Cited by 55 publications

(42 citation statements)

References 23 publications

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“…Ion transfer polarograms Previous voltammetric and polarographic works on the ion transfers of various ions at the W/0 interface have demonstrated that the ion transfer processes of most of ions studied in the following are fast and controlled by the diffusion of the ions in W and/or O [5,6,16]. The polarogram for a reversible transfer reaction (1) of an ion, iZ, at the W/O interface and its half-wave potential.…”

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

“…Hence, the voltammogram will be called as the polarogram hereafter. The procedure, apparatuses and chemicals used for the measurement of polarograms were identical with those described in previous works [5,6,16].The potential in the present work are referred to an imaginary potential denoted as TPhE, where the transfer Gibbs energy, AGtr, corresponds to zero and is dete ned on the basis of the extrathermodynamic assumption that the standard transfer Gibbs energies, AGtra, of TPh s+ and TPhB-across a liquid/liquid interface are equal [16].All data given in this paper were obtained at 25 ± 0.5 °C. …”

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confidence: 99%

“…The VICTLLI has been employed so far for the investigations of the potential generating process in an ion-selective electrode [3,4], relation between the ion transfer at the aqueous(W)/organic(0) interface and the characteristic of the ion [5,6], the solvent extraction mechanisms [7][8][9], the effect of temperature [10] or coexisting salts[11] on the ion transfer, the electron transfer at the W/O interface[12J, the interaction between the ion transfer and the electron transfer [13], the potential oscillation at W/O or W/membrane interface [14,15], etc.…”

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Voltammetric Analysis of Chemical Reactions at Liquid/Liquid or Liquid/Membrane Interfaces

et al. 1991

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The voltammetry for the charge transfer at the liquid/liquid interface, VICTLLI, is demonstrated to be very useful for the analysis of reactions at liquid/liquid or liquid/membrane interfaces, choosing distribution processes of ions at the aqueous/organic interface as examples among many interfacial reactions.(1) The extraction constant in the ion-pair extraction, Kex, is related quantitatively to the half-wave potential in the voltammogram for the reversible ion transfer, and the effect of characteristics of the objective ions on Kex is considered on the basis of the results given by VICTLLI. (2) The distribution of ions in the presence of interfacial redox reactions is discussed referring to the voltammograms for the ion and the electron transfer at an aqueous/organic interface. The distribution depends on the ratio of redox agents available for the electron transfer in the aqueous and/or in the organic as well as on standard transfer energies for both transfers. The interaction between the ion and the electron transfers is also discussed from the viewpoint of the separation of ions. Key words charge transfer voltammogram, ion transfer, electron transfer, distribution of ion, liquid/liquid interfaceThe voltammetry for the charge (ion or electron) transfer at the liquid/liquid interface, VICTLLI, is a most promising method of elucidating the electrochemical features of the charge transfers across the interface because of the advantage that the transferring charge can be specified from the potentials where the voltammogram appears and the number of charges transferred can be determined from the current simultaneously [l,2].The VICTLLI has been employed so far for the investigations of the potential generating process in an ion-selective electrode [3,4], relation between the ion transfer at the aqueous(W)/organic(0) interface and the characteristic of the ion [5,6], the solvent extraction mechanisms [7][8][9], the effect of temperature[10] or coexisting salts[11] on the ion transfer, the electron transfer at the W/O interface[12J, the interaction between the ion transfer and the electron transfer[13], the potential oscillation at W/O or W/membrane interface [14,15], etc.In the present paper, we focus our attention on the distribution of ions in the ion-pair extraction and that coupled with the electron transfer among many interfacial reactions as mentioned above, and elucidate the distribution processes with the aid of VICTLLI. EXPERIMENTALThe charge transfer voltammograms in the present work were recorded by the current-scan polarography at the electrolyte solution dropping electrode [16]. Hence, the voltammogram will be called as the polarogram hereafter. The procedure, apparatuses and chemicals used for the measurement of polarograms were identical with those described in previous works [5,6,16].The potential in the present work are referred to an imaginary potential denoted as TPhE, where the transfer Gibbs energy, AGtr, corresponds to zero and is dete ned on the basis of the extrathermodynamic assum...

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

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Voltammetric Analysis of Chemical Reactions at Liquid/Liquid or Liquid/Membrane Interfaces

et al. 1991

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“…As the charge in n-alkylammonium ions, CH3(CH2)n-NH3+, are localized on NH3+ group and CH3(CH2)n group is almost neutral [15], the change in AAG°tr with various n can be attributed mainly to the change 1n 4G 501v(non-el) [16]. The changes of i\G rr with n observed using w containing MgC12 of various concentrations are plotted in Fig.S.…”

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Salt Effect on the Transfer of Ions at Liquid/Liquid Interface Studied by Polarography With Aqueous Electrolyte Dropping Electrode

et al. 1991

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-The ion transfer polarography was applied to investigate the dissolved state of a diluted ion, i Z, which is rather hydrophobic, in an aqueous solution in the presence of concentrated hydrophilic ions. The effect of coexisting ions on the dissolved states of iZ was evaluated based on the electrostatic and non-electrostatic contributions on the solvation energy of i z and ion-pair formation of iz with a coexisting counter ion. The change in the electrostatic contribution was attributed to the dehydration of iz resulted from the decrease of water activity due to the hydration of the coexisting ions. The change in the non-electrostatic contribution was explained by the variation of the cavity formation energy and the dispersion force with the change of the concentration of coexisting ions. The ion-pair formation of iZ with the coexisting ion is more serious when iZ is more hydrophobic. Key wordsVoltammetry for ion transfer at liquid/liquid interface, salt effect, water activity, ion-pair formation, dispersion forceThe structure of concentrated electrolyte solutions has been studied using Raman spectrum [1-3], NMR [4], neutron diffraction [5] etc.. These methods have been applied to the investigation of the properties of the bulk of the solution, and the dehydration followed by the ion-pair formations in salt solution has been clarified. The methods are not adequate, however, for the investigation of the effect of coexisting salts on the behavior of a diluted ion, iZ, in a solution, The methods employed in such investigations so far have been colorimetry [6] or polarography at the dropping mercury electrode [7]. The voltammetry for the ion transfer at the interface of two immiscible electrolyte solutions, VITIES, has unmatched advantage that the transfer energy, and the number of ions transferred at the aqueous(w)/organic(org) interface can be measured simultaneously [$]. The VITIES is applicable to the transfer of diluted i Z from w to org in the presence of concentrated electrolyte in w.In the present work, half-wave potentials, zV112, for the transfer of various iZ from w to org have been investigated by current scan polarography with the electrolyte solution dropping electrode which is the one of the branch of VITIES, and the effects of kind of coexisting salt and their concentration, cs~lt, on the dissolved state of iZ are discussed based on AV112. EXPERIMENTAL Polarogruphic measurementThe current-scan polarograms were recorded according to the procedure described previously [S]. As coexisting salts which worked also as supporting electelectrolytes, SE, in w, M C12, Mg(NO )2: CaC12, CaBr2, Ca(N03)2 andSrCl2 were examined. The or ptoYd was 2-nitroProPane, NP, into which 0.03 M ,~ crystalviolet tetraphenylborate, CW•TPhB-, was added as SE. The dielectric constant (e) of NP is high enough to dissolve and dissociate the ions under investigation. Since the density of NP is smaller than w, the descending water dropping electrode [S] was employed in the present work. When iZ were alkali metal, alkaline eart...

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Regular Irregularity in the Transfer of Anionic Surfactant across the Liquid/Liquid Interface

et al. 2003

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Irregular current spikes and other anomalies seen in voltammetry of the transfer of anionic surfactants, alkyl sulfonates, and alkyl sulfates across the 1,2-dichloroethane/water (DCE/W) interface are reproducible. The anomalies have a certain regularity that is predicted by a recently proposed concept, the electrochemical instability. Irregular current spikes follow after the augmentation of the current induced when the phase-boundary potential is brought close to the mid-point potential of the transferring surfactant ions. Potential-step chronoamperometry clearly demonstrates the presence of the instability window, that is, the potential region where the interface becomes unstable only in the limited range of the phase-boundary potential.

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The transfer of carboxylate and sulphonate anions at the aqueous/organic solution interface studied by polarography with the electrolyte solution dropping electrode

Cited by 55 publications

References 23 publications

Voltammetric Analysis of Chemical Reactions at Liquid/Liquid or Liquid/Membrane Interfaces

Voltammetric Analysis of Chemical Reactions at Liquid/Liquid or Liquid/Membrane Interfaces

Salt Effect on the Transfer of Ions at Liquid/Liquid Interface Studied by Polarography With Aqueous Electrolyte Dropping Electrode

Regular Irregularity in the Transfer of Anionic Surfactant across the Liquid/Liquid Interface

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