A feasible, fast and reliable method for estimating ion-site association constants in plasticized PVC ion-selective electrode membranes

Siamionau, Andrei V.; Ragoyja, Ekaterina G.; Егоров, В. В.

doi:10.1016/j.aca.2022.340556

Cited by 5 publications

(11 citation statements)

References 24 publications

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“…It is worth noticing that in PVC membranes plasticized with oNPOE, a cation-exchanger forms fairly strong associates with metal cations with association constants 25 ≈ n × 10 3 , while the ion-exchanger salt with amine protonated form is almost completely dissociated. Thus, none of the considered models provides an adequate description of the real situation as in the case of pH UDL .…”

Section: ■ Materials and Methodsmentioning

confidence: 99%

“…Ion association constants for inorganic cations with TClPB – were taken from ref . Ion association constants of protonated cations of ionophores with inorganic anions were estimated by the reference ion method . A tetraphenyl borate anion was used as the reference ion (see Supporting Information III and IV).…”

Section: Methodsmentioning

confidence: 99%

“…To the best of our knowledge, there has been no attempt to perform such computations for the absence of reliable values of parameters required for numerical calculations. Recently, feasible methods for the experimental estimation of singleion partition coefficients 32 and ion association constants 25 were proposed. These parameters were estimated for a number of widely spread ions in PVC membranes plasticized with oNPOE.…”

mentioning

confidence: 99%

“…Taking into account the association constant values for the PVC plasticized membranes estimated from the potentiometric data ( n × 10 1 to n × 10 6 M –1 ), − the specific association model seems to be the most justified. In such a case, generalized description of membrane potential can be obtained using the multispecies approach, suggested by Mikhelson et al − This model accounts for all the possible particles in the membrane, i.e., amine molecular form, free ions and ion pairs for the main membrane components and extractable ions.…”

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confidence: 99%

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H⁺-Selective Electrodes Based on Amine-Type Ionophores: Generalized Theory and A Priori Quantification of Lower and Upper Detection Limits

2023

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A critical analysis of the known theories of functioning of H+-selective electrodes (H+-SEs) based on neutral amine-type carriers is given. A model of specific ion association is proposed, according to which, in membranes plasticized with 2-nitrophenyloctyl ether, the protonated ionophore and cation-exchanger form much stronger ion pairs with inorganic ions extracted from the sample solution than with each other, and simple equations that describe the lower and upper limit detection (pHUDL and pHLDL) are obtained. A feasible and reliable method for quantifying the pK a values of ionophores in the membrane phase from potentiometric data is substantiated. The efficiency of using single-ion partition coefficients and ion pair formation constants for a priori quantitative description of the H+-SE response in solutions of various compositions has been demonstrated for the first time. It is shown that the width of the dynamic response range of such electrodes depends on the nature of the tertiary amino group, and the reasons for the observed effect are discussed.

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Section: ■ Materials and Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

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confidence: 99%

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confidence: 99%

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H⁺-Selective Electrodes Based on Amine-Type Ionophores: Generalized Theory and A Priori Quantification of Lower and Upper Detection Limits

2023

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“…The association constants of cations with TClPB − anion were obtained by the specially developed reference ion technique [ 50 ]. The method is based on the fact that TBA + ion forms no associates with the ion exchanger in the membrane phase and thus can be taken as a reference ion.…”

Section: Table A1mentioning

confidence: 99%

Determination of Single-Ion Partition Coefficients between Water and Plasticized PVC Membrane Using Equilibrium-Based Techniques

Siamionau

Егоров

2022

Membranes

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An experimentally simple method for the direct determination of single-ion partition coefficients between water and a PVC membrane plasticized with o-NPOE is suggested. The method uses the traditional assumption of equal single-ion partition coefficients for some reference cation and anion, in this case tetraphenylphosphonium (TPP+) and tetraphenylborate (TPB−). The method is based on an integrated approach, including direct study of some salts’ distribution between water and membrane phases, estimation of ion association constants, and measurements of unbiased selectivity coefficients for ions of interest, including the reference ones. The knowledge of distribution coefficients together with ion association constants allows for direct calculation of the multiple of the single-ion partition coefficients for the corresponding cation and anion, while the knowledge of unbiased selectivity coefficients together with ion association constants allows for immediate estimation of the single-ion partition coefficients for any ion under study, if the corresponding value for the reference ion is known. Both potentiometric and extraction studies are inherently equilibrium-based techniques, while traditionally accepted methods such as voltammetry and diffusion are kinetical. The inner coherent scale of single-ion partition coefficients between water and membrane phases was constructed.

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Ion exchanger‐based electrodes for determination of highly lipophilic physiologically active amines: Peculiarities of functioning and ways for improving analytical characteristics

Salih,

Novakovskii,

Zakhvitsevich

et al. 2024

Electroanalysis

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A feasible, fast and reliable method for estimating ion-site association constants in plasticized PVC ion-selective electrode membranes

Cited by 5 publications

References 24 publications

H⁺-Selective Electrodes Based on Amine-Type Ionophores: Generalized Theory and A Priori Quantification of Lower and Upper Detection Limits

H⁺-Selective Electrodes Based on Amine-Type Ionophores: Generalized Theory and A Priori Quantification of Lower and Upper Detection Limits

Determination of Single-Ion Partition Coefficients between Water and Plasticized PVC Membrane Using Equilibrium-Based Techniques

Ion exchanger‐based electrodes for determination of highly lipophilic physiologically active amines: Peculiarities of functioning and ways for improving analytical characteristics

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A feasible, fast and reliable method for estimating ion-site association constants in plasticized PVC ion-selective electrode membranes

Cited by 5 publications

References 24 publications

H+-Selective Electrodes Based on Amine-Type Ionophores: Generalized Theory and A Priori Quantification of Lower and Upper Detection Limits

H+-Selective Electrodes Based on Amine-Type Ionophores: Generalized Theory and A Priori Quantification of Lower and Upper Detection Limits

Determination of Single-Ion Partition Coefficients between Water and Plasticized PVC Membrane Using Equilibrium-Based Techniques

Ion exchanger‐based electrodes for determination of highly lipophilic physiologically active amines: Peculiarities of functioning and ways for improving analytical characteristics

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Product

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H⁺-Selective Electrodes Based on Amine-Type Ionophores: Generalized Theory and A Priori Quantification of Lower and Upper Detection Limits

H⁺-Selective Electrodes Based on Amine-Type Ionophores: Generalized Theory and A Priori Quantification of Lower and Upper Detection Limits