1997
DOI: 10.1021/ac960891m
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Determination of Unbiased Selectivity Coefficients of Neutral Carrier-Based Cation-Selective Electrodes

Abstract: A new procedure for the determination of selectivity coefficients of neutral carrier-based cation-selective electrodes is established that avoids exposure to the preferred ion prior to the measurement of discriminated ions. The method is, therefore, unbiased by the presence of preferred ions in the membrane that otherwise could mask the response to discriminated ion solutions. It is generally applicable as long as a series of considerations are met and can only be applied once for a given membrane. Careful stu… Show more

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Cited by 362 publications
(356 citation statements)
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“…This process leads to a bias in the detection limit and in the calculated selectivity coefficients that can amount to many orders of magnitude. 25,27,28 The selectivity bias can be quite easily eliminated by various means, including the use of ion buffers in the sample, 29 membranes that have not been exposed to the most preferred ions before characterization, 30 and membranes that exhibit a siphoning effect in direction of the inner solution. 31 Selectivity coefficients obtained with any of these methodologies often reflect a much better selectivity than with traditional, biased protocols.…”
Section: Detection Limitmentioning
confidence: 99%
“…This process leads to a bias in the detection limit and in the calculated selectivity coefficients that can amount to many orders of magnitude. 25,27,28 The selectivity bias can be quite easily eliminated by various means, including the use of ion buffers in the sample, 29 membranes that have not been exposed to the most preferred ions before characterization, 30 and membranes that exhibit a siphoning effect in direction of the inner solution. 31 Selectivity coefficients obtained with any of these methodologies often reflect a much better selectivity than with traditional, biased protocols.…”
Section: Detection Limitmentioning
confidence: 99%
“…Unbiased selectivity coefficients can be obtained either by measuring the calibration curves for discriminated ions before the first contact of the membrane with the primary ion [27] or by using appropriate inner solutions [28]. The response slopes for the interfering ions must be recorded since close to theoretical values confirm that selectivity coefficients are not biased [29].…”
Section: Introductionmentioning
confidence: 99%
“…The present results for K ij « 1 document that selectivity coefficients near the hypothetical equilibrium values can be realized only at the highest sample activities. At lower activities, the selectivity behavior is usually far from the thermodynamically controlled domain, unless the studied ISE membrane has initially not been prepared with the respective interfering ion j instead of the primary ion i [36]. This holds at least for relatively short measurements.…”
Section: Resultsmentioning
confidence: 99%