The influence of the plasticizer nature on the selectivity of ion-selective electrodes to physiologically active amine cations: Regularities and abnormalities

The influence of the nature of plasticizer in the membrane of an ion-selective electrode (ISE) on its selectivity to cations of more than 20 physiologically active amines (PAA) is studied. It is found that an increase in the basicity of the plasticizer leads to a sharp increase in the membrane selectivity to PAA cations with lower degrees of the substitution of the salt-forming nitrogen atom, and also to PAA cations with nonionic polar groups capable of forming hydrogen bonds with Lewis bases. PAA cations forming intermolecular hydrogen bonds are an exception. The effect of the nature of the ion exchanger on the selectivity to PAA cations is strongest when plasticizers with low basicity are used; the selectivity of membranes with plasticizers of high basicity does not depend on the nature of the ion exchanger. For ISEs based on the neutral carrier dibenzo-18-crown-6 (DB-18-C-6), the best selectivity to primary amine cations in comparison to secondary and tertiary ones is achieved using plasticizers with low basicity.     

Ion-selective electrodes for determination of organic ammonium ions: Ways for selectivity control

The influence of the ISE membrane composition on the selectivity for primary, secondary, tertiary, and quaternary alkylammonium cations, as well as for cations of physiologically active amines, has been investigated. Factors studied include the effect of plasticizer (2-nitrophenyl octyl ether, o-NPOE; dibutyl phthalate, DBP; dinonyl adipate, DNA; tris(2-ethylhexyl) phosphate, TEHP) and ion exchanger (potassium tetrakis(4-chlorophenyl)borate, K(TpClPB); potassium tris(nonyloxy)benzenesulfonate, K(TNOBS)), as well as that of the lipophilic cationic additive (tetradecylammonium nitrate, (TDA)NO(3)) and neutral carrier (dibenzo-18-crown-6) presence in membrane. It has been established that plasticizer nature affects K(i,j)(pot) values both when the target and/or foreign ions have non-ionic polar groups capable of specific interaction with plasticizer, and when the only difference consists in the substitution degree of their ionic groups. K(i,j)(pot) values for quaternary alkylammonium cations over primary-tertiary ones change in the following order: TEHP>DBP approximately DNA>o-NPOE. The highest K(i,j)(pot) value change is achieved for the primary-quaternary alkylammonium cation pair, amounting to 3 and 4.7 orders for membranes containing K(TNOBS) and K(TpClPB) as ion exchangers, respectively. In its turn, the ion exchanger influence on the selectivity depends on plasticizer nature, it being maximal for o-NPOE (about 2 orders) and practically non-existent for TEHP. On the whole, as compared to K(TpClPB)-based ISEs, those based on K(TNOBS) show higher selectivity for primary-tertiary alkylammonium cations over quaternary ones. Incorporation of (TDA)NO(3) into membrane causes further improvement of selectivity for primary-tertiary alkylammonium cations in the case of K(TNOBS) only. The maximal total effect of the ion exchanger and lipophilic ionic additive is observed for ISEs with DNA-plasticized membranes and is over 3 orders. The influence of crown ether on the selectivity also depends significantly upon ion exchanger and plasticizer nature. For ISEs with o-NPOE-plasticized membranes the K(i,j)(pot) value changes can be as great as 3 (ion exchanger K(TNOBS)) and even 4.5 (ion exchanger K(TpClPB)) orders. On the contrary, for ISEs with TEHP-plasticized membranes the crown ether effect on the selectivity is unessential. The results obtained are explained by peculiarities of organic ammonium cations solvating by plasticizer and association of cations with ion exchangers.     

Lipophilic ionic additive for controlling the selectivity of ion-selective electrodes reversible to cations of nitrogen-containing organic bases

The effect of a lipophilic ionic additive, a tetradecylammonium salt of a liquid ion exchanger, on the selectivity of ion-selective electrodes (ISEs) for cations of nitrogen-containing organic bases was studied. Additive-containing ISEs exhibited a higher selectivity for cations of primary to tertiary amines as compared to that for quaternary ammonium cations. A maximum change in selectivity (up to more than two orders of magnitude) due to the introduction of tetradecylammonium was observed for membranes containing dinonyladipate as a plasticizer and tris(nonyloxy)benzene sulfonic acid as an ion exchanger. In this case, the introduction of lipophilic ionic additive may lead to the reversal of the selectivity series. The effect of the lipophilic ionic additive on the selectivity of ISEs with membranes plasticized with o-nitrophenyl octyl ether decreased approximately by an order of magnitude. The selectivity of ISEs with the membranes containing tetrakis(4-chlorophenyl) borate as a cation exchanger was virtually independent of the presence of lipophilic ionic additives. The results obtained were explained by the peculiarities of ion-pair formation in the membrane.     

Some ion exchange properties of amorphous titanium (IV) phosphate

An amorphous titanium (IV) phosphate exchanger has been synthesised and characterized through elemental analysis, infrared, and thermogravimetric techniques. Divalent cations Mn, Co, Ni, Cu, Zn, Cd, Hg and Pb in bidistilled water have been exchanged with the proton of the exchanger matrix using a batch method. From these results the thermodynamic selectivity constants and distribution coefficients were calculated, whose values indicate a high selectivity for Pb and Hg. Both cations were successfully separated from a mixture containing all cations studied through column separation experiments.     

Hyamine 1622 - Selective PVC Membrane Electrodes Based on bis (Crown Ether)s

Abstract

Hyamine 1622 - selective PVC membrane electrodes based on bis (crown ether)s containing the benzo - 18 - crown - 6 moiety were prepared, using o - nitrophenyloctylether (NPOE) or dipentylphthalate (DPP) as the plasticizer of the PVC membrane. Selectivity coefficients for various interfering ions (inorganic and organic cations), were determined by the mixed solution method. The selectivity of the respective electrodes was found to be affected by the kind of plasticizer employed, and NPOE seemed to be a more suitable plasticizer than DPP. The NPOE electrode system based on the bis (crown ether) that has 11 atoms between the two benzo-18-crown-6 moieties offers the advantage of greater selectivity. The electrodes show excellent electrode properties, and the electrode response was stable in a wide pH range.     

Ion-exchange selectivity of a sulfonic cation exchanger based on immobilized cis-tetraphenylcalix[4]resorcinolarene

The ion-exchange equilibrium of protons in SO₃H groups of a sulfonic cation exchanger based on immobilized cis-tetraphenylcalix[4]resorcinolarene with cations of Li⁺, Na⁺, Ag⁺, Cu²⁺, In³⁺, and protonated 1,3,5,7-tetraazaadamantane in aqueous solutions of electrolytes at 293 K was studied. The corrected coefficients of the cation exchange selectivity were calculated.     

The effect of the ion exchanger site-counterion complex formation on the selectivities of ISEs

Using the model of ideally associated solution, the effect of ion association of the ion exchanger sites with main and foreign counterions on the selectivity of ISEs based on liquid ion exchangers has been considered. Equations which describe the potentiometric selectivity coefficient as a function of ion association constants in the membrane phase and of standard free energies of transfer of the determined and foreign ions from water to the membrane are obtained for the following main cases: (a) the determined and foreign ions are single-charged; (b) the determined ion is double-charged and the foreign ion is single-charged. It is shown that in the case of single-charged main and foreign ions, the ratio of the ion association constants has a great effect on the potentiometric selectivity of membranes, only if the ion exchanger sites produce less strong associates with the determined counterion as compared with the foreign one. Otherwise, this effect is insignificant. The selectivity for double-charged ions should increase, other things being equal, as the first constant of association of these ions with the ion exchanger sites increases. The effect of producing ion triplets of the type I(2)R((+/-)) on the selectivity of ISEs is also considered. Experimental data are presented which illustrate the effect of the nature of the ion exchanger on the potentiometric selectivity. Some procedures employing the factor of ion association for increasing the potentiometric selectivity of liquid ion exchange membranes are considered.     

Wire-coated silver(I) ion-selective electrode based on 2-mercaptobenzothiazole (MBT) ionophore: application to the determination of silver in real samples.

A new wire-coated silver ion-selective electrode with a wider concentration range (10(-7) M - 10(-1) M) was developed using 2-mercaptobenzothiazole (MBT) as a neutral ionophore. An optimum mixture of PVC, ionophore, dioctylphtalate (DOP) as a plasticizer and sodium tetraphenylborate (NaTPB) as an ion-pairing agent was used in preparing the coatings. The effect of various parameters, such as the electrode bed nature, coating composition and solution pH, on the efficiency of the electrode is described. It has been shown that platinum acts as a more suitable bed for electrode preparation, and exhibits a slope of 59.5 +/- 1 mV over the whole range of studied concentrations. The selectivity coefficient of the electrode towards various interfering cations as well as its reproducibility, response time and lifetime of the electrode were estimated. The developed electrode was successfully used for the determination of trace amounts of silver in human hair and photographic waste as real samples and in the potentiometric titration of halides as an indicator electrode.     

Solid-contact ion-selective electrodes for aromatic cations based on pi-coordinating soft carriers

Ion-selective electrodes (ISEs) based on pi-coordinating carriers were prepared and investigated as potentiometric sensors for aromatic cations, using N-methylpyridinium as a model aromatic cation. Derivatives of tetraphenylborate were studied as charged carriers in plasticized poly(vinyl chloride) membranes. Furthermore, neutral compounds containing pi-coordinating anthryl groups were studied as neutral carriers. Bis(2-ethylhexyl)sebacate (DOS) and 2-nitrophenyl octyl ether (o-NPOE) were used as non-polar and polar plasticizer, respectively. ISEs were constructed by using poly(3,4-ethylenedioxythiophene) (PEDOT) as solid-contact material. Conventional ISEs with internal filling solution were used for comparison. The potentiometric responses of the ISEs were investigated using N-methylpyridinium as primary ion. The results show that the selectivity of the ISEs is influenced significantly by both the plasticizer and the charged carriers, while the neutral carriers studied have only a minor influence on the selectivity. The role of cation-pi interactions between aromatic cations and the membrane components is discussed.     

Sorption of M(III) with KFP-12 Phosphonic Cation Exchanger from Chloride Solutions

Sorption by KFP-12 phosphonic anion exchanger of ions of triply charged metals, such as indium, gallium, yttrium, and iron, from chloride solutions was studied. The nature of bonding between sorbed cations and functional groups of the cation exchanger and the mechanism of the ion exchange reaction were elucidated.     

Copper-Selective Electrode in the Analysis of Dye-Containing Solutions

The effect of dye concentrations in solutions on the potential of a copper-selective electrode with a chalcogenide membrane was studied. It was found that the electrode potential depends on the dye concentration in solutions containing no copper ions. Conventional selectivity coefficients of the electrode with respect to dye anions were determined. The selectivity coefficients ambiguously changed with the dye nature and their concentration in solutions. The use of the calibration graph method without taking into account the composition of the test solution gave rise to great errors in the results of determinations.     

Sorption of Cs<Superscript>+</Superscript> and Sr<Superscript>2+</Superscript> by ion exchanger based on titanium phosphate

Sorption capacity of a composite ion exchanger based on titanium phosphate for Cs⁺ and Sr²⁺ cations was studied. The effect of pH and concentration of salts and, in particular, sodium chloride in solution on the sorption efficiency and distribution coefficient was analyzed. The diffusion coefficients were calculated for the Cs⁺ and Sr²⁺ cations and the time of half-exchange of the Na⁺ cation for the Cs⁺ and Sr²⁺ cations was found.     

Sorption behavior of gamma-irradiated silica gel

The effect of Pb(II) and non-ionic surfactants (oxyethylate alcohols OS-10 and ALM-10) on the rate of intraparticle diffusion and on to the equilibrium sorption on Purolite C 106 cation exchanger in hydrogen form was investigated. The sorption of Pb(II) cations and in free state and bonded to the surfactant was measured. The coefficients of intraparticle diffusion were also calculated.     

Novel Anion Exchangers for Electrodes with Improved Selectivity to Divalent Anions

It has been found that replacing of several long‐chain alkyl substituents at the nitrogen atom of lipophilic quaternary ammonium salts (QAS) by methyls results in a dramatic increase of the potentiometric selectivity of ion‐selective electrodes (ISE) with QAS‐based plasticized PVC membranes to some divalent anions against the monovalent ones. The discussed effect of QAS cation nature on the potentiometric selectivity is also partly retained for ISE with neutral carrier‐based membranes doped with QAS to provide anion permselectivity. This opens up new possibilities to control the potentiometric selectivity of ISE for divalent anions by the appropriate selection of the anion exchanger.     

A Clotrimazole-Selective Electrode and its Application to Pharmaceutical Analysis

The effect of measurement conditions and the nature of the plasticizer of an ion-selective electrode membrane (ortho-nitrophenyloctyl ether, dinonyl adipate, dibutyl phthalate) on the main performance characteristics of clotrimazole-selective electrodes with polyvinyl chloride ion-exchange membranes containing potassium tetrakis(4-chlorophenyl)borate as an ion exchanger was studied. The introduction of small (up to 20%) ethanol additives into the aqueous solution leads to a significant improvement of the potential stability and expands the working range of the electrodes. All of the studied electrodes have high selectivity to clotrimazole with respect to both inorganic and organic cations, slope of the electrode function close to the theoretical value, and low limits of detection (5.0 × 10^–8–7.5 × 10^–8 M). An electrode with a membrane plasticized with ortho-nitrophenyloctyl ether was the best for the combination of characteristics. It was demonstrated that clotrimazole can be determined in model solutions and various dosage forms (spray, cream, suppositories, tablets) using direct potentiometry and potentiometric titration with sodium tetraphenylborate. The proposed procedures are rapid (10–15 min) and characterized by excellent reproducibility (the relative standard deviation does not exceed 1.2%).     

A study of the influence of modifying iron and aluminum chloride additives on the water-absorbing capacity and thermal stability of peat

The influence exerted by modifying additives of inorganic nature on the hydrophilicity of peats from the Orlovskoe deposit in Tomsk oblast and on their thermal stability was studied. The acid-base, equilibrium, and kinetic properties of the starting peat samples and those modified with solutions of iron(III) and aluminum chlorides were examined. Their physicochemical parameters were determined: total exchange capacity, acidity by acid and basic groups, relative humidity, distribution coefficients, effective diffusion coefficients, and activation energy. The effect of modifying cations on the thermal decomposition of peat was analyzed.     

Ion-exchange behaviour of copper ferricyanide

A new inorganic ion exchanger, copper ferricyanide prepared by adding copper nitrate to a potassium ferricyanide solution at 80°C has been found to be stable in acids and salt solutions. It has been characterized by chemical analysis, thermogravimetry. X-ray and infrared spectroscopy. Distribution coefficients determined for various metal ions show that the exchanger has a high affinity for heavy univalent cations. The variation of K_d for a number of metal ions as a function of nitric acid concentration and ammonium nitrate has been investigated to elucidate the probable exchange mechanism and to work out conditions for elution. Binary separations of Cs from a number of other metal ions were achieved on the column of exchanger. The exchanger is useful for the separation of¹³⁷Cs.     

Ion selectivity obtained under voltammetric conditions when a TCNQ chemically modified electrode is presented with aqueous solutions containing tetraalkylammonium cations

The voltammetry of 7,7,8,8-tetracyanoquinodimethane (TCNQ) at an electrode-microparticle-aqueous (electrolye) interface has been proposed as a cation sensor on the basis that changes in electrolyte cation (analyte) concentrations result in reproducible shifts in the TCNQ0/- reversible potential. In order to probe the ion selective nature of the TCNQ sensor, the voltammetric response towards a series of tetraalkylammonium cations of variable size and hydrophobicity were studied. Both the thermodynamics (reversible potential) and kinetics (voltammetric peak separation) of the TCNQ0/- system were strongly dependant on the identity of the R4N+ cation. The reversible potential responded in a Nernstian manner to changes in cation concentration. When presented with mixed-analyte solutions, the TCNQ system exhibited Nicolsky type (or competitive) form of selectivity. However, the selectivity coefficients found in the present study were far greater than previously reported with group I cations. The order obtained for the tetraalkylammonium series indicates that ion selectivity is predominantly based on analyte solvation thermodyanics rather than a specific ionophore mechanism.     

Flocculation of starch-coated solidified emulsion droplets and calcium carbonate particles

Zirconium phosphate (ZrP) has recently been demonstrated as an excellent sorbent for heavy metals due to its high selectivity, high thermal stability, and absolute insolubility in water. However, it cannot be readily adopted in fixed beds or any other flowthrough system due to the excessive pressure drop and poor mechanical strength resulting from its fine submicrometer particle sizes. In the present study a hybrid sorbent, i.e., polymer-supported ZrP, was prepared by dispersing ZrP within a strongly acidic cation exchanger D-001 and used for enhanced lead removal from contaminated waters. D-001 was selected as a host material for sorbent preparation mainly because of the Donnan membrane effect resulting from the nondiffusible negatively charged sulfonic acid group on the exchanger surface, which would enhance permeation of the targeted metal ions. The hybrid sorbent (hereafter denoted ZrP-001) was characterized using a nitrogen adsorption technique, scanning electron microscope (SEM), and X-ray diffraction (XRD). Lead sorption onto ZrP-001 was found to be pH dependent due to the ion-exchange mechanism, and its sorption kinetics onto ZrP-001 followed the pseudo-first-order model. Compared to D-001, ZrP-001 exhibited more favorable lead sorption particularly in terms of high selectivity, as indicated by its substantially larger distribution coefficients when other competing cations Na(+), Ca(2+), and Mg(2+) coexisted at a high level in solution. Fixed-bed column runs showed that lead sorption on ZrP-001 resulted in a conspicuous decrease of this toxic metal from 40 mg/L to below 0.05 mg/L. By comparison with D-001 and ZrP-CP (ZrP dispersion within a neutrally charged polymer CP), enhanced removal efficiency of ZrP-001 resulted from the Donnan membrane effect of the host material D-001. Moreover, its feasible regeneration by diluted acid solution and negligible ZrP loss during operation also helps ZrP-001 to be a potential candidate for lead removal from water. Thus, all the results suggested that ZrP-001 offers excellent potential for lead removal from contaminated water.     

Cross-sensitive chemical sensors based on tetraphenylporphyrin and phthalocyanine

The properties of solvent polymeric membrane sensors based on 5,10,15,20-tetraphenylporphyrin (TPP) and phthalocyanine (PHC) have been investigated. The sensitivity and selectivity of sensors towards wide range of mono- and di-valent cations have been measured. The selectivity towards the transition metal ions for TPP-based sensor does not correspond to the cation lipophilicity sequence. The dependence of response on pH was studied. The cross-sensitivity parameters, including average response slope, signal-to-noise ratio and “non-selectivity” factor for all sensors were calculated and compared. The influence of plasticizer and ionic additive on the response of sensors was characterized using principal component analysis (PCA).