On the selection of the optimal plasticizer for calix[n]arene-based ion-selective electrodes: Possible correlation between the ion selectivity and the ?softness? of the plasticizer

Sakaki, Takeshi; Harada, Takaaki; Kawahara, Yohko; Shinkai, Seiji

doi:10.1007/bf00707133

Cited by 17 publications

(9 citation statements)

References 9 publications

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“…The overall precision of extraction results attains some ±0.2 kJ/mol (with exception of H + ), whereas mean values from electrochemical measurements do not exceed a precision of ±1 kJ/mol. The obtained extraction results are corroborated by almost complete agreement with electrochemical values obtained with PVC membrane . Calculated values in a paper 27 reasonably agree with the extraction data.…”

Section: Resultssupporting

confidence: 80%

“…Dioctyl Sebacate, DOS. This is another solvent largely used in ISEs aimed at measurements of cation concentrations, e.g., its selectivity in the absence of any cation complex-forming agent was measured for alkali metal cations . The selectivity span is much lower than that for NPOE, and reported values read from Figure of ref are about log K pot Na,M = 0.4 for Cs + and as low as ca.…”

Section: Resultsmentioning

confidence: 93%

“…h Ref . i Ref ; selectivity calculated from selectivity electrochemical coefficient log K pot Na,M after conversion to K (Cs + /M + ) and referred to Δ t G ° , *(Cs + ) = 22.9 kJ/mol, the values were read off from Figure of the reference. j Ref .…”

Section: Resultsmentioning

confidence: 99%

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Gibbs Energies of Transfer of Alkali Metal Cations between Mutually Saturated Water−Solvent Systems Determined from Extraction Experiments with Radiotracer ¹³⁷Cs

2006

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Thermodynamic standard Gibbs energies of transfer of alkali metal cations related to Cs+ cation [DeltatG degrees*,(Cs+)-[DeltatG degrees*,(M+)] between several mutually saturated solvents of the type water-solvent were calculated from determined extraction exchange constants Kexch degrees,*(Cs+/M+). The used liquid-liquid extraction method with radioactive tracing by 137Cs permits attaining higher precision of the values as compared to the methods used up to now. The data for o-nitrophenyloctyl ether, 1,2-dichloroethane, and 1-octanol were compared with literature sources and recommended absolute values of DeltatG degrees,*M+) are reported. For dissociating solvents, the dependences of [DeltatG degrees,*(Cs+) - [DeltatG degrees,*(M+)] on Gibbs energy of hydration of an ion, DeltaGhydr degrees are straight lines either for four cations Cs+, Rb+, K+, and Na+ (nitrosolvents) or for three cations Cs+, Rb+, and K+ (1,2-dichloroethane and 1-octanol). The hydration of Na+ and still more of Li+ in the water-saturated organic phase is apparent from the results. This manifests for high-water-content equilibrium 1-octanol even in a reversal of the values [i.e., DeltatG degrees*,(Li+) being more negative than DeltatG degrees,*(Na+)], although for Cs+, Rb+, and K+, the general trend is conserved. Water-saturated 1-octanol is thus slightly less basic than water, but the overall selectivity is very low. For one studied nondissociating solvent, dioctyl sebacate, the trend of the dependences of log Kexch degrees,*(CsB/M+) on DeltaGhydr degrees is similar to that of Kexch degrees,*(Cs+/M+) for polar solvents, but different for different anions B, thus reflecting ion association in the organic phase.

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Section: Resultssupporting

confidence: 80%

Section: Resultsmentioning

confidence: 93%

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Gibbs Energies of Transfer of Alkali Metal Cations between Mutually Saturated Water−Solvent Systems Determined from Extraction Experiments with Radiotracer ¹³⁷Cs

2006

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“…Additionally, the membrane plasticizer can also have a dramatic effect on both the upper and lower detection limits of ISEs [19]. Several studies have examined the effects of plasticizers on the potentiometric performance of ISEs [18,20,21].…”

Section: Introductionmentioning

confidence: 99%

Potentiometric Response Characteristics of Membrane-BasedCs+-Selective Electrodes Containing Ionophore-Functionalized Polymeric Microspheres

Peper

Gonczy

2011

International Journal of Electrochemistry

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Cs + -selective solvent polymeric membrane-based ion-selective electrodes (ISEs) were developed by doping ethylene glycolfunctionalized cross-linked polystyrene microspheres (P-EG) into a plasticized poly(vinyl chloride) (PVC) matrix containing sodium tetrakis-(3,5-bis(trifluoromethyl)phenyl) borate (TFPB) as the ion exchanger. A systematic study examining the effects of the membrane plasticizers bis(2-ethylhexyl) sebacate (DOS), 2-nitrophenyl octyl ether (NPOE), and 2-fluorophenyl nitrophenyl ether (FPNPE) on the potentiometric response and selectivity of the corresponding electrodes was performed. Under certain conditions, P-EG-based ion-selective electrodes (ISEs) containing TFPB and plasticized with NPOE exhibited a super-Nernstian response between 1 × 10 −3 and 1 × 10 −4 M Cs + , a response characteristic not observed in analogous membranes plasticized with either DOS or FPNPE. Additionally, the performance of P-EG-based ISEs was compared to electrodes based on two mobile ionophores, a neutral lipophilic ethylene glycol derivative (ethylene glycol monooctadecyl ether (U-EG)) and a charged metallacarborane ionophore, sodium bis(dicarbollyl)cobaltate(III) (CC). In general, P-EG-based electrodes plasticized with FPNPE yielded the best performance, with a linear range from 10 −1 -10 −5 M Cs + , a conventional lower detection limit of 8.1 × 10 −6 M Cs + , and a response slope of 57.7 mV/decade. The pH response of P-EG ISEs containing TFPB was evaluated for membranes plasticized with either NPOE or FPNPE. In both cases, the electrodes remained stable throughout the pH range 3-12, with only slight proton interference observed below pH 3.

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“…It has been asserted that these observations are due to the differences in polarity or dielectric constants (ε NPOE,mem =14, ε DOS,mem = 4.8) of the two types of plasticized PVC membrane [32,33,34]. Alternatively, a study of the effect of more than 15 plasticizers on the selectivity of ISEs constructed from the same ionophore demonstrated a relationship between the hard/soft character of the plasticizing molecules and observed selectivity [35]. Similar influences have been observed for detection limits and degrees of ion pairing, with both parameters being dependent on the nature of the plasticizer employed [29,36,37].…”

Section: Components Of Ion-selective Electrodesmentioning

confidence: 91%

Ionophore-based ion-selective potentiometric and optical sensors

2003

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This paper describes ion-selective electrodes (ISEs) and optodes with a focus on the fundamental mechanisms, response characteristics, and recognition elements (ionophores) described to date for these sensors. The topics covered review the most frequently encountered ideas about ionophore-based sensors, including the theoretical and experimental parameters that influence response, typical ionophore structures, useful membrane compositions, and applications. Since these sensors are applicable in a number of fields, such as clinical, environmental, and process monitoring, as well as more novel approaches such as microfluidic-based systems and micro/nanoprobes, this article provides descriptions that are oriented toward a more general audience. Furthermore, a large portion of this review describes the ionophore component itself in hopes of inspiring ideas in readers of how novel molecular architectures with new ionic targets or improved selectivity can be developed.

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On the selection of the optimal plasticizer for calix[n]arene-based ion-selective electrodes: Possible correlation between the ion selectivity and the ?softness? of the plasticizer

Cited by 17 publications

References 9 publications

Gibbs Energies of Transfer of Alkali Metal Cations between Mutually Saturated Water−Solvent Systems Determined from Extraction Experiments with Radiotracer ¹³⁷Cs

Gibbs Energies of Transfer of Alkali Metal Cations between Mutually Saturated Water−Solvent Systems Determined from Extraction Experiments with Radiotracer ¹³⁷Cs

Potentiometric Response Characteristics of Membrane-BasedCs+-Selective Electrodes Containing Ionophore-Functionalized Polymeric Microspheres

Ionophore-based ion-selective potentiometric and optical sensors

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On the selection of the optimal plasticizer for calix[n]arene-based ion-selective electrodes: Possible correlation between the ion selectivity and the ?softness? of the plasticizer

Cited by 17 publications

References 9 publications

Gibbs Energies of Transfer of Alkali Metal Cations between Mutually Saturated Water−Solvent Systems Determined from Extraction Experiments with Radiotracer 137Cs

Gibbs Energies of Transfer of Alkali Metal Cations between Mutually Saturated Water−Solvent Systems Determined from Extraction Experiments with Radiotracer 137Cs

Potentiometric Response Characteristics of Membrane-BasedCs+-Selective Electrodes Containing Ionophore-Functionalized Polymeric Microspheres

Ionophore-based ion-selective potentiometric and optical sensors

Contact Info

Product

Resources

About

Gibbs Energies of Transfer of Alkali Metal Cations between Mutually Saturated Water−Solvent Systems Determined from Extraction Experiments with Radiotracer ¹³⁷Cs

Gibbs Energies of Transfer of Alkali Metal Cations between Mutually Saturated Water−Solvent Systems Determined from Extraction Experiments with Radiotracer ¹³⁷Cs