Micro-hole interface for the amperometric determination of ionic species in aqueous solutions

Osborne, M.C.; Shao, Yuanhua; Pereira, Carlos M.; Girault, Hubert H.

doi:10.1016/0022-0728(93)02941-a

Cited by 107 publications

(48 citation statements)

References 14 publications

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“…They are often correlated with biological and pharmacological activity, such as adsorption, cell membrane permeability and hydrophobic binding. 4,5 Although large and significant progress has been achieved in the last decade, [6][7][8][9][10][11][12][13][14][15][16][17][18][19][20] standard Gibbs energies of transfer of many common inorganic ions are still not available. 6 One reason for this situation are the limitations of the four-electrode technique.…”

Section: Introductionmentioning

confidence: 99%

“…As a consequence, in some cases less reliable data have been reported in the literature, with values of DG falling close to the end of the potential window. Recent modifications in the four-electrode technique allowed an expansion of the potential window in ITIES experiments by measurements at microhole interfaces [7][8][9][10][11][12] or indirectly by coupling of chemical equilibria in both phases. 7,[17][18][19][20] However, the non-polarizability of some organic solvents (e.g.…”

Section: Introductionmentioning

confidence: 99%

“…they are more reliable. 2,[6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22] The electrochemical technique introduced by one of us 24 and successfully applied to a number of systems [25][26][27][28][29] explores a so called '' three-phase electrode '' and conventional threeelectrode instrumentation. With this technique standard Gibbs energies for the water/nitrobenzene system can be determined in the range from À41 to +37 kJ mol À1 , 28 without coupling of solution equilibria.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

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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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

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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“…11,12 These methods were applied to the investigation of the relation between potential difference, E, at the W/O interface and the current, I, flowed across the interface. Controlled potential difference electrolysis at the W/O interface, 13 CPDE, was carried out in the identification of the product of the interfacial charge transfer reaction.…”

Section: Methods For Measurements Of Charge Transfer Reactions At Thementioning

confidence: 99%

Biomimetic Charge Transfer Reactions at the Aqueous/Organic Solution Interface or through Artificial Membrane

et al. 2012

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Some biomimetic reactions observed with the aid of aqueous/organic, W/O, two phases or liquid membrane, LM, systems were introduced. The reactions introduced were mostly those reported by the group of present authors as follows; (1) (5) A new type of membrane transport reaction realized in the presence of an applied electrical potential gradient parallel to the W/ membrane interface. The processes of above-described reactions were elucidated based on the voltammetric methods and concepts taking into account the properties common to both artificial LMs and biomembranes. A method proposed by present authors for the elucidation of the membrane transport process was also introduced.

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“…3. The microholes, bored into the film by an ultraviolet laser photoablation technique (Laserx Co., Ltd.), 6 were employed as micro-ITIESs. The film was tightly held between two silicon rubber sheets together with the two compartments with screws.…”

mentioning

confidence: 99%

Determination of the Standard Entropy Changes of Ion Transfer for 1-Alkylpyridinium Ions by Thermal Modulation Voltammetry with Laser Heating at a Water/1,2-Dichloroethane Interface

et al. 2014

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When laser light impinges upon a liquid-liquid interface between an optically transparent aqueous and opaque organic phase from the aqueous to organic phase, the temperature at the interface and the interfacial region rises. Using this rise in temperature, we have proposed and developed thermal modulation voltammetry at an interface between two immiscible electrolyte solutions (TMV-ITIES) and have determined the standard entropy changes of ion transfer, ∆S ,O→W tr . In this work, we have determined ∆S ,O→W tr for four 1-alkylpridinium ions, namely 1-methylpyridinium ion (MePy + ), 1-ethylpyridinium ion (EtPy + ), 1-propylpyridinium ion (PrPy + ), and 1-buthylpyridinium ion (BuPy + ) by TMV-ITIES. As a result, we obtained the ∆S ,O→W tr values of 108.0 ± 0.5 (n = 3), 75.8 ± 4.4, 55.6 ± 1.2, and 42.7 ± 0. Keywords Thermal modulation voltammetry, laser heating, water/1,2-dichloroethane interface, standard entropy change, ion transfer, 1-alkylpridinium ion (TM) voltammograms. A diode-pumped solid-state laser (DPSS, Phototechnica, JST, 532 nm, 30 mW) was used as a heating source. This laser beam was electronically modulated at 10 Hz by using a function synthesizer (NF, 1915), and was introduced from the aqueous to organic phase. The electrolytic cell was machined from poly(chlorotrifluoroethylene) resin blocks and composed of two compartments for the aqueous and 1,2-dichloroethane (DCE) phase. The cell was placed in a shield case in order to maintain the temperature and avoid electric noise. The two compartments were separated by a thin polyester film 16 μm thick with approximately 120 microholes 30 μm in diameter arranged as in Fig. 3. The microholes, bored into the film by an ultraviolet laser photoablation technique (Laserx Co., Ltd.), 6 were employed as micro-ITIESs. The film was tightly held between two silicon rubber sheets together with the two compartments with screws. As shown in Scheme 1, the aqueous phase contained 10 mmol dm -3 (mM) LiCl as a supporting electrolyte and X mmol dm -3 1-alkylpridinium ion as a sample, while the DCE phase contained 10 mmol dm -3 crystalviolet tetrakis(4-cholorophenyl)borate (CVTClPB), which served not only as a supporting electrolyte but also as an optically absorbing substance. A visible absorption spectrum of CVTClPB in DCE showed the absorption maximum at 591 nm and a molar absorption coefficient at 532 nm was 3.3 × 10 3 m 2 mol -1 . When the laser beam was modulated at 10 Hz, the temperature at the interface and interfacial region was also modulated, and consequently a current for ion transfer was modulated at the same frequency, depending on the standard entropy change of ion transfer and a temperature coefficient of a diffusion coefficient of a transferring ion. The modulated current was detected with a four-electrode type potentiostat (Hokuto Denko, HA1010mM1A) and amplified with a two-phase lock-in amplifier (NF, 5584A). The reference signal was supplied from the function synthesizer, which was used for driving the DPSS laser. The potential was swept at 5 mVs -1 with ...

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Micro-hole interface for the amperometric determination of ionic species in aqueous solutions

Cited by 107 publications

References 14 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

Biomimetic Charge Transfer Reactions at the Aqueous/Organic Solution Interface or through Artificial Membrane

Determination of the Standard Entropy Changes of Ion Transfer for 1-Alkylpyridinium Ions by Thermal Modulation Voltammetry with Laser Heating at a Water/1,2-Dichloroethane Interface

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