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成人, 出来; 政憲, 大多和; 幸雄, 金治

doi:10.1246/nikkashi.1979.1623

Cited by 4 publications

(4 citation statements)

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“…Although aqueous solutions with extremely high concentrations have been studied for about half a century, [1][2][3][4] the attention to highlyconcentrated aqueous solutions has revived within this decade. The expansion of the potential window to ca.…”

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confidence: 99%

Basal-Plane Orientation of Zn Electrodeposits Induced by Loss of Free Water in Concentrated Aqueous Solutions

Inoguchi

Kitada

Fukami

et al. 2020

J. Electrochem. Soc.

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Concentrated aqueous solutions attract considerable attention because water electrolysis can be suppressed due to a decrease in the amount of free water. The present study focuses on electrodeposition behaviors of metallic zinc (Zn) using concentrated aqueous solutions containing bis(trifluoromethylsulfonyl)amide (Tf2N–) anions. An increase in Tf2N– concentration significantly enhances water-anion interactions, giving characteristic infrared spectra for the breakdown of the hydrogen-bonding networks of water clusters, i.e. loss of free water. For the Tf2N– system Zn electrodeposits with the preferred orientation of hcp basal plane was observed, while, for the SO4 2– system with the presence of the hydrogen-bonding networks, preferred orientation of basal plane was not observed. The preferred orientation of basal plane is not attributed to the adsorption of Tf2N– anions on the electrode, proved by the use of mixed Zn(Tf2N)2-ZnSO4 concentrated solutions. The loss of free water in the concentrated Zn(Tf2N)2 solutions will suppress hydrogen adsorption at the cathode to promote surface diffusion of intermediate Zn+ adions and growth of Zn crystals. Consequently, the promotions and the easier growth of Zn basal planes with the lowest interfacial free energy will enhance the horizontal growth of Zn basal planes.

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confidence: 99%

Basal-Plane Orientation of Zn Electrodeposits Induced by Loss of Free Water in Concentrated Aqueous Solutions

Inoguchi

Kitada

Fukami

et al. 2020

J. Electrochem. Soc.

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“…The procedure for the preparation of CV+ TPhB-was identical to that mentioned previously [6]. The purification of NP was achieved by passing through a column of activated alumina.…”

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confidence: 99%

“…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 [$].…”

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confidence: 99%

“…The potential in the present work is referred to an imaginary potential denoted as TPhE where the transfer free energy of an ion at w/NP interface is equal to zero on the asis f n extrathermodYnamic assumption [9]. A11 measurements were carried out at 25±0.5 C. ChemicalsThe procedure for the preparation of CV+ TPhB-was identical to that mentioned previously [6]. The purification of NP was achieved by passing through a column of activated alumina.…”

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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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Ion transfer at the interface between an aqueous solution in the presence of concentrated salts and an organic solution studied by polarography at the electrolyte solution dropping electrode

Ogura

Kihara

Suzuki

et al. 1993

Journal of Electroanalytical Chemistry

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Cited by 4 publications

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Basal-Plane Orientation of Zn Electrodeposits Induced by Loss of Free Water in Concentrated Aqueous Solutions

Basal-Plane Orientation of Zn Electrodeposits Induced by Loss of Free Water in Concentrated Aqueous Solutions

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

Ion transfer at the interface between an aqueous solution in the presence of concentrated salts and an organic solution studied by polarography at the electrolyte solution dropping electrode

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