Effects of Lipophilic Charged Sites on the Electromotive Behavior of Liquid Membrane Electrodes

Pretsch, Ernö; Wegmann, Dorothée; Ammann, D.; Bezegh, Andras.; Dinten, O.; Läubli, Markus W.; Morf, Werner E.; Oesch, U.; Sugahara, Kiyoshi; Weiss, H.; Simon, W.

doi:10.1007/978-3-642-70518-2_3

Cited by 9 publications

(4 citation statements)

References 3 publications

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“…On the other hand, anion-exchanger membranes are known to exhibit similar characteristics in zero-current potentiometry. A higher ion-exchanger concentration in the membrane results in a more theoretical slope while low concentrations may more easily give slopes lower than Nernstian, especially for anions of limited lipophilicity [17]. The reason for this behavior may be related to additional transient transport phenomena or interferences, but have not clearly been elucidated in the literature.…”

Section: Resultsmentioning

confidence: 97%

Pulsed chronopotentiometric membrane electrodes based on plasticized poly(vinyl chloride) with covalently bound ferrocene functionalities as solid contact transducer

Pawlak

Grygołowicz‐Pawlak

Bakker

2012

Pure and Applied Chemistry

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Ion-selective membrane materials based on poly(vinyl chloride) (PVC)-containing covalently attached redox-active ferrocene (Fc) groups are characterized here as all-solidstate pulsed voltammetric ion sensors. The redox capacity of the membrane increases 7-fold with a doubling of the Fc content and 3-fold with the addition of 10 wt % of the lipophilic electrolyte ETH 500, tetradodecylammonium tetrakis(4-chlorophenyl)borate. This salt improves the ionic conductivity of the membrane and appears to make the Fc groups electrochemically more accessible. A too high content of the two, on the other hand, was found to cause undesired sensitivity to redox-active species present in the sample solution. Dilution of the membrane with a plasticizer eliminated this redox sensitivity while preserving its high redox capacity. A practical application of the designed electrodes in electrochemical analysis was demonstrated with a multi-pulse protocol that includes a current-controlled ion uptake pulse, followed by an open-circuit potential (OCP) measurement and a regeneration pulse. Potentiometric calibration curves obtained with this protocol exhibited a linear response with near-Nernstian slopes for acetate, nitrate, chloride, and perchlorate ions with the selectivity expected for an ion-exchanging membrane.

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Section: Resultsmentioning

confidence: 97%

Pulsed chronopotentiometric membrane electrodes based on plasticized poly(vinyl chloride) with covalently bound ferrocene functionalities as solid contact transducer

Pawlak

Grygołowicz‐Pawlak

Bakker

2012

Pure and Applied Chemistry

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“…Moreover, it is known that ion-exchangers also decrease membrane resistance, [32], reduce response time [33]. and have a selectivity-modifying influence based on their ion-exchange properties and concentration in the membrane [34].…”

Section: Ion Exchanger Selectionmentioning

confidence: 99%

Trace‐Level Determination of Cs⁺ Using Membrane‐Based Ion‐Selective Electrodes

et al. 2006

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A membrane-based ion-selective electrode (ISE) has been developed for the trace-level determination of Cs þ in aqueous samples. A systematic evaluation of several ionophores was performed, examining the effect of membrane plasticizer and ion exchanger on sensor selectivity. Poly(vinyl chloride) (PVC)-based ion-selective membranes of conventional composition containing calix[6]arene hexaacetic acid hexaethylester as ionophore (Cs I, 10 mmol/kg), bis(2-ethylhexyl) sebacate (DOS, 66 wt%) as plasticizer, and undecaiodinated closo-dodecacarborane (UIC, 4.1 mmol/kg) as ion exchanger exhibited superior performance with respect to selectivity over alkali and alkaline earth metal cations. The unbiased selectivity coefficients, log K ) were determined to be À 2.9, À 4.7, À 8.5, and À 8.7, respectively. DOS-plasticized PVC electrodes containing Cs I and UIC were optimized for trace-level measurements, exhibiting a lower detection limit of 7.9 Â 10 À9 M Cs þ (log a Cs,LDL ¼ À 8.1) in the presence of a 1 Â 10 À5 M Na þ background. The utility of the optimized ISEs was demonstrated by determining the concentration of Cs þ in both drinking water and natural water samples.

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“…8 Several methods have been reported for the determination of QnCl including spectrophotometry, [9][10][11] chromato-graphy [12][13][14][15] and fluorometry. 16 The present work describes new selective membrane electrodes of the conventional type, for the determination of QnCl in pure solution and in pharmaceuticals preparations.…”

Section: Introductionmentioning

confidence: 99%

Energy‐Dispersive and X‐Ray Photoelectron Spectroscopy and Electron Microscopy of New Quininium‐Plastic Membrane Electrodes

2007

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New quininium (Qn) plastic membrane electrodes of the conventional type were constructed and characterized. They are based on incorporation of Qn-reineckate (QnRn) ion-pair, Qn-phosphotungstate (Qn3-PT), or Qn-phosphomolybdate (Qn3PM) ion associate into a poly(vinyl chloride) membrane. The electrodes are selective for Qn and have been successfully used for the determination of Qn2SO4 in pharmaceutical tablets. Nevertheless, they showed, as almost all other ion-selective electrodes, limited life times. Energy dispersive- (EDS) and X-ray photoelectron spectroscopy (XPS), as well as electron microscopy were applied to investigate the cause of this limitation in the life times of the electrodes. The results indicated that the electrodes lose their activity after prolonged soaking as a result of leaching of the ion exchanger from the membranes into the test solution in addition to deformation at the surface of the expired electrode.

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Effects of Lipophilic Charged Sites on the Electromotive Behavior of Liquid Membrane Electrodes

Cited by 9 publications

References 3 publications

Pulsed chronopotentiometric membrane electrodes based on plasticized poly(vinyl chloride) with covalently bound ferrocene functionalities as solid contact transducer

Pulsed chronopotentiometric membrane electrodes based on plasticized poly(vinyl chloride) with covalently bound ferrocene functionalities as solid contact transducer

Trace‐Level Determination of Cs⁺ Using Membrane‐Based Ion‐Selective Electrodes

Energy‐Dispersive and X‐Ray Photoelectron Spectroscopy and Electron Microscopy of New Quininium‐Plastic Membrane Electrodes

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Effects of Lipophilic Charged Sites on the Electromotive Behavior of Liquid Membrane Electrodes

Cited by 9 publications

References 3 publications

Pulsed chronopotentiometric membrane electrodes based on plasticized poly(vinyl chloride) with covalently bound ferrocene functionalities as solid contact transducer

Pulsed chronopotentiometric membrane electrodes based on plasticized poly(vinyl chloride) with covalently bound ferrocene functionalities as solid contact transducer

Trace‐Level Determination of Cs+ Using Membrane‐Based Ion‐Selective Electrodes

Energy‐Dispersive and X‐Ray Photoelectron Spectroscopy and Electron Microscopy of New Quininium‐Plastic Membrane Electrodes

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Trace‐Level Determination of Cs⁺ Using Membrane‐Based Ion‐Selective Electrodes