Sodium Ion-Selective Chalcogenide Glass Electrodes

Abstract

Analytical characteristics and sensing mechanism of sodium ion-selective electrodes based on NaCl-Ga₂S₃-GeS₂ glasses have been investigated. Chalcogenide glass electrodes containing 10 mol.% NaCl in the membrane showed near-Nernstian response in the concentration range from 10-³ to 1 M sodium nitrate solution. These sensors were superior to the conventional pNa oxide glass electrodes in selectivity in the presence of hydrogen ions and in Na⁺ ion sensitivity in fluoride media. Prolonged solution treatment for several days reduces, however, the detection limit of the sensors and the slope of the electrode response. Ionic processes at the membrane surface have been investigated using XPS technique and ²²Na tracer measurements. It was shown that sodium ion-exchange governed Na⁺ ion response of chalcogenide     

Nitrate-containing ionic liquids as active membrane components of nitrate-selection electrodes

Two dialkylimidazolium nitrate ionic liquids (ILs) have been tested for use as an active component of plasticized PVC membranes in nitrate ion selective electrodes (ISEs). The potentiometric reversibility and the main electrochemical characteristics of the ISEs in KNO₃ solutions have been studied. The test membranes contain 5% of the active component and demonstrate a near-Nernstian response to NO ₃ ^? . The use of a more hydrophobic IL based on dioctadecylimidazolium increases the sensitivity and decreases the detection limit: the slope of the electrode function is 57 mV/pC, and C _min = 3.7 · 10^?6 mol/L. The pH range of the membrane performance has been studied, and the potentiometric selectivity to NO ₃ ^? in the presence of several foreign anions has been determined. The new electrode exceeds the commercially available analogue (an ELIT 021 nitrate-selective electrode) in the detection limit and response time. The utility of the new electrode for the direct potentiometric determination of nitrate ILs in aqueous solutions has been demonstrated.     

Long-chain tetraalkyltin compounds as neutral carriers for nitrite-selective PVC membrane electrodes

The nitrite-selective PVC membrane electrodes prepared with lipophilic long-chain tetraalkyltin compounds as neutral carrier show selectivity patterns significantly different from those obtained with classical anion-exchangers. The potentiometric selectivity coefficient for nitrite ion with respect to nitrate ion has been improved by about four orders of magnitude. The linear response range of the electrode based on tetralauryltin (TLT) is from 1 × 10^?1M down to 2×10^?5M with a detection limit of 5 × 10^?6M. The Nernstian response of the electrode in the medium of pH≥7 gradually changes to a doubled super-Nernstian response when the solution turns slightly acidic. The change of the response slope has a closely relation with the stepwise complex-formation equilibrium of the carrier with the anion involved, which was experimentally studied by using ultraviolet spectroscopy. An explanation of the anomalous response behavior as well as the curve form of the potential-pH plot is given.     

Membrane-dialyzer injection loop for enhancing the selectivity of anion-responsive liquid-membrane electrodes in flow systems Part 2. A selective sensing system for salicylate

An electrode-based flow-injection system suitable for the direct determination of salicylic acid is described. The system utilizez a tubular polymer membrrane electrode based on manganese(III) tetraphenylporphyrin chloride to sense salicylate ions formed in a recipient buffer solution held within the upper channel of a flow-through membrane dialyzer assembly. Samples containing salicylic acid are manually intoduced into the lower channel of the dialysis unit, in which a thin silicone rubber membrane separates the two channels. The analyte is trapped across the membrane as salicylate ions within a static layer of an appropriate recipient buffer. After a fixed trapping time, the recipient plug is flushed to the electrode in a conventional flow-injection manner. Peak potentials observed are logarithmically related to the salicylic acid concentrations in the original sample. Without the dialysis unit, the electrode response to salicylate is nearly Nernstian over the range 2 × 10^?6?10^?2 M. In the complete flow/dialysis system, near Nernstian response was achieved for 10^?4?10^?2 M salicylate with a 2-min trapping time. Detection limits can be altered by changing the trapping time. Anionic salicylate can be determined by acidifying the sample. The resulting system offers very high selectivity for salicylate (as salicylic acid) over most inorganic and organic anions normally found in blood. Preliminary studies demonstrate the practical application of this system for the determination of salicylate in serum.     

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.     

Sequential injection analysis of chloride and nitrate in waters with improved accuracy using potentiometric detection

Accurate simultaneous analysis of different anionic species using ion-selective electrodes (ISEs) can be achieved even for non-specific sensors by resorting to an ordinary least squares multiple regression in the vicinity of the predicted concentrations. In this work the potentialities of this approach are evidenced by the determination of nitrate and chloride in synthetic and real water samples in which chloride concentration was significantly higher than nitrate. An AgCl/Ag₂S electrode based on a homogeneous crystalline membrane together with a PVC electrode based on tert-octylammonium bromide dissolved in dibutylphthalate were used as potentiometric detectors for chloride and nitrate, respectively. For the implementation of the procedure, an automatic system based on sequential injection analysis was used. The results obtained by the standard addition method were biased for low concentrations of nitrate and were dependant on the relative proportion of NO₃⁻/Cl⁻. The results obtained by the proposed methodology for chloride determination were slightly better when compared to those obtained by the standard addition method. In relation to nitrate determination, the proposed methodology yielded values with a relative root mean square error of prediction (RRMSEP) of 2.8%, while for standard addition calibration, mean error values were approximately 12.1%.     

Use of a flow-injection system in the evaluation of the characteristic behavior of neutral carriers in lithium ion-selective electrodes

A flow-injection system based on microconduits is used to investigate electrode characteristics such as selectivity, detection limit, and response and equilibrium times of the new ionophore, N,N,N′,N′-tetraisobutyl-5,5-dimethyl-3,7-dioxanonane diamide, in lithium ion-selective electrodes. These characteristics were compared with those of the ionophore N,N′-diheptyl-N,N′,5,5-tetramethyl-3,7-dioxanone diamide. The new ionophore has superior detection limits and shorter response and equilibrium time, but the other exhibits better selectivity for lithium with respect to sodium. Values of K^Pot_LiNa for the new ionophore vary from 0.0450 to 0.566, depending on the methods of measurement and solution conditions. This phenomenon is discussed. Stop-flow experiments effectively demonstrated the response and equilibrium time differences between these two ionophore membranes.     

Flow-through calcium-selective electrode: application in flow-injection analysis and ion chromatography

The use of solid contact flow-through calcium-selective electrodes as potentiometric detectors in flow-injection analysis and non-suppressed ion chromatography is discussed. Owing to the high selectivity of the membrane electrode based on tetratolyl-m-xylylenediphosphine dioxide, it can be used to monitor trace amounts of calcium ions in the presence of a 100-fold excess of alkali metal, ammonium and magnesium ions. The detection limit is about 1 × 10^?6 M. The composition and thickncss of the calcium selective membrane influence both the detection limit and selectivity of the electrode. The sensitivity of this potentiometric detector in ion chromatography relative to alkaline earth and heavy metals is significantly higher than that of a commercial conductivity detector.     

Highly selective PVC-membrane electrodes based on Co(II)-Salen for determination of nitrite ion.

A cobalt(II) derivative was used as a suitable ionophore for the preparation of a polymeric membrane nitrite-selective electrode. The electrode reveals a Nemstian behavior over a very wide NO2- ion concentration range (1.0 x 10(-6)-1.0 x 10(-1) M) and a very low detection limit (5.0 x 10(-7) M). The potentiometric response is independent of the pH of solution in the pH range 4.0-9.5. The electrode shows advantages such as low resistance, fast response and, most importantly, good selectivity relative to a wide variety of inorganic and organic anions. In fact, the selectivity behavior of the proposed NO2- ion-selective electrode shows great improvements compared to the previously reported electrodes for nitrite ion. The proposed electrodes could be used for at least 2 months without any significant changes in potentials. The electrode was successfully applied to the determination of nitrate ion concentrations in sausage and milk samples.     

A tetra-coordinate nickel(II) complex as neutral carrier for nitrate-selective PVC membrane electrode

The potentiometric response properties and applications of a tetra-coordinate nickel(II) complex with relatively high selectivity toward nitrate ion are described. The nickel(II) complex of 5,7,12,14-tetramethyl-1,4,8,11-tetraazacyclotetradeca-4,6,11,13-tetraene was used as a neutral carrier into plasticized poly(vinyl chloride) (PVC) membrane. The influence of several variables was investigated in order to optimize the potentiometric response and selectivity of the electrode. The resulting membrane electrode incorporating 31.0% PVC, 61.0% dioctyl phthalate (DOP) as plasticizer, 3% methyltrioctylammonium chloride (MTOAC) as a cationic additive and 5% carrier (all w/w) demonstrates a Nernstian response slope of −59.6 mV per decade over the concentration range of 5×10⁻⁶-1×10⁻¹ M NO₃⁻. The electrode exhibits a fast response time (≤10 s), a detection limit of 2.5×10⁻⁶ M, and can be used over a wide pH range of 4-12. The electrode shows improved selectivity in comparison to most of the previously reported nitrate-selective electrodes. It was successfully applied to the determination of nitrate ion in natural water samples.     

A lead(II)-selective PVC membrane based on a Schiff base complex of N,N'-bis(salicylidene)-2,6-pyridinediamine

PVC membrane electrodes for lead ion based on N,N’-bis(salicylidene)-2,6-pyridinediamine as membrane carrier were prepared. Among their membranes, a membrane electrode (m-3) containing o-NPOE as a plasticizer and 50 mol% additive displays an excellent Nernstian response (29.4 mV/decade) and the limit of detection of −log a (M) = 6.04 to Pb²⁺ in Pb(NO₃)₂ solutions at room temperature. It has a rapid response time within 10 s over the entire concentration range. The proposed electrode revealed good selectivity and response for Pb²⁺ over a wide variety of other metal ions in a pH 5.0 buffer solutions, and good reproducibility of base line in subsequent measurements.     

Calixazacrown ethers for copper(II) ion-selective electrode

Five novel 1,3-alternate calix[4]azacrown ethers having 2-picolyl, 3-picolyl, and benzyl unit on the nitrogen atom were synthesized and used as ionophores for transition metal-selective polymeric membrane electrodes. The electrode based on 2-picolyl armed 1,3-alternate calix [4] azacrown ether exhibited Nernstian response toward copper (II) ion over a concentration range (10(-4.5) M-10(-2.5) M). The detection limit was determined as 10(-5) M in pH 7 and the selectivity coefficients for possible interfering cations were evaluated. Anions in the sample solution strongly affected the electrode response.     

Influence of Aprotic Solvent on Selectivity of an Amperometric Sensor with Nafion Membrane

This paper presents the results of investigation on selectivity of the sulfur dioxide amperometric sensor with Nafion membrane in the presence of carbon monoxide and nitrogen dioxide as the interferents. There have been compared selectivity coefficients, for the sensors containing the following internal electrolytes: solution of sulfuric acid (concentration 5 mol dm^?3) in pure water (A) and solution of sulfuric acid (concentration 5 mol dm^?3) in mixed solvent dimethylsulfoxide‐water with an DMSO: H₂O mole ratio of 1 : 2 (B). Values of the selectivity coefficients have been calculated based on the calibration curves. Analysis of both calibration curves and selectivity coefficients plays a significant role in optimization of a working point of a particular sensor. The investigated sensor operates in a three‐electrode system, where the working and counter electrodes are vacuum sublimation deposited on the membrane surface.     

Gas-diffusion separation and flow injection potentiometry

Summary The similarities and differences of the operation principle of gas-sensing electrodes and potentiometric detection coupled to gas-diffusion separation in flow injection analysis are discussed with special emphasis on selectivity and sensitivity aspects. Several examples of application are presented highlighting the improvements in detectability obtained by gas-diffusion flow injection potentiometry. High sensitivity determination of ammonium is achieved through accumulation of ammonia released from the sample stream in the small recipient volume of the gas-diffusion unit. A method for almost specific determination of cyanide is presented making use of gas-diffusion separation of hydrogen cyanide and potentiometric detection with a selective AgI membrane electrode. The interference of sulfide is totally prevented by its oxidation in the donor line. If applied to potentiometric measurement following gas diffusion separation an intrinsically non-selective metallic silver wire electrode turns out to enable the selective detection of sulfide with high sensitivity and fast response. A new approach for diffusive sampling and on-line detection of gas-phase contaminants is exemplified by the determination of NO_x.     

Construction and assessment of some perchlorate-selective liquid membrane electrodes

Perchlorate-selective liquid membrane electrodes were developed by incorporating the ion-pair complexes of perchlorate with brucine, cinchonidine, emetine and benzyldimethyltetradecylammonium chloride (zephiramine) in nitrobenzene. The electrodes, which respond to perchlorate ion over the concentration range 1.0–5.0 × 10^?4 M ClO^?₄, have a fast response and wide pH range. The zephiramine-perchlorate electrode was the best in terms of its fast response, wide pH range and high reproducibility of potentials. Most common inorganic and organic anions, except permanganate, do not cause significant interference. Electrodes based on brucine-, emetine- and zephiramine-perchlorate were successfully employed for the direct potentiometric determination of perchlorate in the presence of halides, sulphate, nitrate and chlorate. The cinchonidine-perchlorate electrode showed comparatively poor selectivity.     

Enhancement of selectivity of a benzoate-sensitive liquid membrane electrode by alkylphenol

The selectivity of the benzoate-sensitive liquid membrane electrode based on tri-n-octylmethylammonium benzoate in o-dichlorobenzene enhanced is remarkably by the addition of p-t-octylphenol to the liquid exchanger solution. There is a linear relationship between the change in the logarithmic selectivity coefficient and the pK_a value of the aliphatic monocarboxylic acid interference. Large decreases in the selectivity coefficients are observed for ions having a small proton acceptor ability such as perchlorate and tri-fluoromethanesulfonate.     

Microband Sensor for As(III) Analysis: Reduced Matrix Interference

A portable sensor based on a microband design for arsenic detection in drinking water is presented. The work was focused to minimize interference encountered with a standard screen‐printed electrodes featuring an onboard gold working electrode, carbon counter and silver−silver chloride pseudo‐reference electrodes as composite coatings on plastic surface. The interference effect was identified as chloride ions interacting with the silver surface of the reference electrode and formation of soluble silver chloride complexes such as AgCl₄³⁻. By modification of the reference electrodes with Nafion membrane (5 % in alcohols), the interference was entirely eliminated. However, membrane coverage and uniformity can impact the electrodes reproducibility and performance. Hence, the sensor design was further considered and a microband format was produced lending favorable diffusive to capacitive current characteristics. Using the microband electrodes allowed As(III) detection with limit of detection of 0.8 ppb (in 4 M HCl electrolyte), inherently avoiding the problems of electrode fouling and maximizing analyte signal in river water samples. This is below the World Health Organization limit of 10 μg L⁻¹ (ppb). The electrolyte system was chosen so as to avoid problems from other common metal ions, most notably Cu(II). The presented electrode system is cost effective and offers a viable alternative to the colorimetric test kits presently employed for arsenic analysis in drinking water.     

Sulfite-sensitive solvent/polymeric-membrane electrode based on bis(diethyldithiocarbamato)mercury(II)

A new solvent/polymeric-membrane electrode which exhibits significant potentiometric response toward sulfite ion in the 1 × 10_?6?1 × 10^?3 M range is described. The membrane is prepared by incorporation of neutral bis(diethyldithiocarbamato)mercury (II) in a thin film of plasticized poly (vinyl chloride). In sharp contrast to classical Hofmeister behavior, the resulting membrane displays little or no response to a wide range of anions (log K^pot_i,j ? ?4, i being sulfite) including sulfate, nitrate, nitrite, chloride, perchlorate, salicylate, and alkylsulfonates. Bromide and thiocyanate are moderate interferents, while significant response to iodide, thiosulfate, and sulfide is observed. These selectivity data, along with other response characteristics of the membrane, are used to postulate the mechanism by which the electrode responds to sulfite. Preliminary studies demonstrate that the electrode can be used in conjunction with an outer gas-permeable membrane for highly selective detection of total sulfite species in the form of sulfur dioxide.     

Nitrite‐Selective Electrode Based On Cobalt(II) tert‐Butyl‐Salophen Ionophore

A series of polymeric nitrite‐selective electrodes containing a new lipophilic ionophore Co(II) tert‐butyl‐salophen is reported. The stability of Co(II) ionophores within a PVC‐based membrane was investigated by leaching experiments. Different membrane compositions were explored in order to reach the lowest possible limit of detection for a PVC‐based nitrite selective polymeric membrane electrode containing this ionophore. The optimal electrode showed a limit of detection of 2×10^?6 M and exhibited four orders of magnitude of discrimination over nitrate, chloride and bromide. The electrodes were evaluated in undiluted human urine and attest to the robustness of the ionophore.