A Reference Electrode System for Electrochemical Measurements in Pure Water

A reference hydrogen electrode systems is constructed by employing a strip of proton‐type Nafion membrane as an ion‐conducting “bridge” to connect a reversible hydrogen electrode (RHE) in an acidic solution to an electrochemical system using pure water as electrolyte, in which the working electrode (WE) is placed. Using such a reference electrode system, the potential at the “WE/pure water” interface is equal to the equilibrium hydrogen electrode potential in pure water when the potential difference between RHE and WE is zero, irrespective of the pH value of the acidic solution in the RHE compartment. The accuracy and reproducibility of the WE potential measurements are within 1–2 mV.     

Direct Writing of Conducting Polymers

Described herein is a new printing method—direct writing of conducting polymers (CPs)—based on pipette‐tip localized continuous electrochemical growth. A single barrel micropipette containing a metal wire (Pt) is filled with a mixture of monomer, supporting electrolyte, and an appropriate solvent. A droplet at the tip of the pipette contacts the substrate, which becomes the working electrode of a micro‐electrochemical cell confined to the tip droplet and the pipette. The metallic wire in the pipette acts as both counter and reference electrode. Electropolymerization forms the CP on the working electrode in a pattern controlled by the movement of the pipette. In this study, various width poly(pyrrole) 2D and 3D structures are extruded and characterized in terms of microcyclic voltammetry, Raman spectroscopy, and scanning electron microscopy.

     

Applicability of 0.05 mol kg(-1) potassium hydrogen phthalate as reference value pH standard in water-organic solvent mixtures

The applicability of 0.05 mol kg(-1) potassium hydrogen phthalate (KHPh(S), S=the solvent under study) as reference value pH standard (RVS) was studied in water-organic solvent mixtures. Phthalic acid in various aqueous organic solvent mixtures was titrated potentiometrically with Bu(4)NOH (MeOH), using a pH-ISFET and a glass electrode as pH-sensors, and the buffer capacity of the HPh(-) solution was roughly estimated from the difference between the first and second half-neutralization potentials. The influence of potassium ion to the buffer capacity was also studied, titrating KHPh and Et(4)NHPh with CF(3)SO(3)H and Bu(4)NOH (MeOH) and comparing the titration curves. The KHPh solution loses its buffer capacity if the solvent mixture has an aprotic property. For aqueous mixtures of protophilic aprotic solvents (e.g. DMSO and DMF), it is unsuitable as RVS if the water content is less than ca. 40 (v/v)%. The necessity of selecting subsidiary pH standard(s) is suggested for the solvent systems in which KHPh is inapplicable.     

Applicability of 0.05 mol kg potassium hydrogen phthalate as reference value pH standard in water–organic solvent mixtures

The applicability of 0.05 mol kg⁻¹ potassium hydrogen phthalate (KHPh(S), S=the solvent under study) as reference value pH standard (RVS) was studied in water–organic solvent mixtures. Phthalic acid in various aqueous organic solvent mixtures was titrated potentiometrically with Bu₄NOH (MeOH), using a pH-ISFET and a glass electrode as pH-sensors, and the buffer capacity of the HPh⁻ solution was roughly estimated from the difference between the first and second half-neutralization potentials. The influence of potassium ion to the buffer capacity was also studied, titrating KHPh and Et₄NHPh with CF₃SO₃H and Bu₄NOH (MeOH) and comparing the titration curves. The KHPh solution loses its buffer capacity if the solvent mixture has an aprotic property. For aqueous mixtures of protophilic aprotic solvents (e.g. DMSO and DMF), it is unsuitable as RVS if the water content is less than ca. 40 (v/v)%. The necessity of selecting subsidiary pH standard(s) is suggested for the solvent systems in which KHPh is inapplicable.     

Capillary zone electrophoresis in non-aqueous solutions: pH of the background electrolyte

Although the establishment of a pH scale and the determination of the pH in water is not problematic, it is not a straightforward task in non-aqueous solvents. As capillary zone electrophoresis (CZE) in organic solvents has gained increasing interest, it seems to be valuable to re-discuss the concept of the pH in such media, especially pointing to those aspects, which make pH measurement uncertain in non-aqueous solvents. In this review, the relevant aspects when dealing with primary standard (PS) and secondary standard (SS) as recommended by the International Union of Pure and Applied Chemistry (IUPAC), and the usage of the operational pH are discussed with special emphasis to non-aqueous solvents. Here, different liquid junction potentials, incomplete dissociation of the electrolytes (especially in solvents with low or moderate relative permittivity) and the occurrence of homo- and heteroconjugation must be taken into account. Problems arising in capillary zone electrophoresis practice are addressed, e.g. when the background electrolyte (BGE) consists of organic solvents, but the measuring electrode (normally the glass electrode) is calibrated with aqueous buffers, and the liquid junction potentials between the solvents do not cancel each other. The alternative concept of establishing a certain pH is described, using mixtures of reference acids or bases with known pKa in the organic solvent, and their respective salts, at a certain concentration ratio, relying to the Henderson-Hasselbalch equation. Special discussion is directed to those organic solvents most common in capillary zone electrophoresis, methanol (MeOH) and acetonitrile (ACN), but other solvents are included as well. The potential significance of small amounts of water present in the organic solvent on changes in pKa values, and thus on the pH of the buffering components is pointed out.     

Improvement of the silver/silver chloride reference electrode and its application to pH measurement

When a silver/silver chloride (Ag AgCl ) reference electrode was used continuously in a low conductivity solution or reductive solution, it was often observed that stability of the liquid junction potential was lost. This phenomenon was remarkable with a Ag AgCl reference electrode compared to a calomel reference electrode. We found that 340 mg l(-1) of silver was dissolved in 3 M potassium chloride (KCl) internal solution as silver complex ions (AgCl(-(x-1))(x)) for x = 2 or 3. However, only 1.93 mg l(-1) of silver chloride (AgCl) can theoretically be dissolved in water. The complex ion that effused into the sample solution through the liquid junction clogged the liquid junction (e.g. porous ceramic) as AgCl, or as metallic silver (Ag) in reducing solution. Therefore, the constant effusion of KCl internal solution was inhibited, and the liquid junction potential became unstable or fluctuating. A new reference electrode was developed, which can eliminate AgCl(-(x-1))(x) in 3 M KCl internal solution by the use of chelating resins. A combination of this reference electrode with a pH electrode made long-term stable pH measurements possible.     

Investigation of a Thin‐film Quasi‐reference Electrode Fabricated by Combined Sputtering‐evaporation Approach

This paper presents the development of a thin‐film quasi‐reference electrode (tQRE), which was fabricated by sputtering silver (Ag) on a conducting gold layer. The Ag layer was subsequently covered by silver chloride (AgCl) with the aid of e‐beam evaporation. The functionality of the tQREs as reliable reference electrodes was confirmed by observing the potential response in solutions with various chloride ion concentrations. The influence of solution pH on the potential change of the tQREs was evaluated. In the solution with controlled ionic strength, the tQREs were able to provide stable and consistent potential outputs. Experimental investigation of the electrochemical sensors with integrated tQREs demonstrated potential applicability of the tQREs to be incorporated into miniaturized and disposable lab‐on‐a‐chip sensors for point‐of‐care/in‐situ measurements.     

Solid contact ion sensor with conducting polymer layer copolymerized with the ion-selective membrane for determination of calcium in blood serum

A new solid contact ion selective electrode with intermediate conducting polymer (CP) layer formed by electropolymerization on a gold electrode of a bifunctional monomer, n-phenyl-ethylenediamine-methacrylamide (NPEDMA), which contains a methacrylamide group attached to aniline, is presented. The conducting polymer was studied by means of optical spectroscopy, cyclic voltammetry and potentiometric measurements. Ca²⁺-ion-selective membrane based on acrylated urethane polymer was shown to co-polymerize with the CP forming highly adhesive boundary that prevents formation of water layers between the CP and membrane, thus enhancing the stability and life-time of the sensor. The designed ion-selective electrode was successfully used for determination of total calcium ion concentration in blood serum samples.     

A potentiometric detector for following pH shifts in liquid chromatography

A potentiometric detector suitable for measurement of pH shifts caused by cation-exchange phenomena in reverse-phase liquid chromatography is described. A capillary flow-through glass pH electrode and a small reference electrode are included in a design that produces reliable results in the acid pH range. The detector is calibrated in the steady-state and dynamic modes with pH reference solutions in water and water-methanol mixtures.     

Application of a Deconvolutive Procedure to Analyze Several Chlorophenol Species in Natural Waters by Square‐Wave Voltammetry on the Boron‐Doped Diamond Electrode

Abstract

The anodic voltammetric behavior of 4‐chlorophenol (4‐CP) on a boron‐doped diamond electrode (BDD) in aqueous solution was studied by square‐wave voltammetry. After optimization of the experimental conditions, 4‐CP was determined in a Britton‐Robinson buffer solution with pH 6.0, prepared with pure water. Moreover, mixtures of some different chlorophenols were also investigated and an analytical method was developed for the simultaneous determination of these compounds in natural waters. The oxidation of 4‐CP on BDD was used for analytical purposes and quantification limits as low as 9.2 µg L^?1 were obtained. This result illustrates the advantage of using oxidation process currents on BDD electrodes as the analytical signal, even in contaminated matrices. In order to compare the results found here with the conventional methodology to determine chlorophenols, HPLC‐UV‐vis measurements were also performed and were in good agreement with the analytical values obtained by SWV.     

Counter-Ion Influence on Polypyrrole Potentiometric pH Sensitivity

The pH sensitivity of conducting polymer films is an important issue from the sensor design point of view. The doping and supporting electrolyte anions effect on the potentiometric sensitivity and response time of polypyrrole (PPy) electrodes towards changes of solution pH were studied. It was found that (i) the response of PPy doped by easily exchangeable common anions (Cl^–, NO₃ ^–, ClO₄ ^–) in their solutions (KCl, KNO₃, NaClO₄) is slow. In contrast, (ii) polypyrrole films deposited in the presence of weak acid anions (phthalates, oxalates, salicylates) were characterised by instantaneous responses in the above mentioned solutions. On the basis of electrochemical experiments (open circuit potential vs. time dependencies, cyclic voltammetry, EQCM), the observed differences were attributed to different mechanisms of pH sensitivity of tested films. The long response times are related to the incorporation of the solution ions into the film in order to compensate charges created due to protonation. On the other hand, if the ion-exchange is hindered as in the case of (ii), instantaneous open circuit responses are observed due to polarisation of the oxidised polymer layer, analogously to the metal electrode. Moreover, for these films the internal pH buffering within the polymer membrane will weaken the pH change effect.The mechanisms were confirmed in the course of studying the pH effect in solutions containing anions easily (KCl, NaClO₄, KNO₃) or hardly exchangeable with polypyrrole (K₂SO₄, sodium poly(4-styrenesulphonate) solutions) acidified with H₂SO₄.     

Redox Properties of the Iron Complexes of Orally Active Iron Chelators CP20, CP502, CP509, and ICL670

Redox cycling of iron is a critical aspect of iron toxicity. Reduction of a low‐molecular‐weight iron(III)‐complex followed by oxidation of the iron(II)‐complex by hydrogen peroxide may yield the reactive hydroxyl radical (OH^.) or an oxoiron(IV) species (the Fenton reaction). Complexation of iron by a ligand that shifts the electrode potential of the complex to either to far below ?350 mV (dioxygen/superoxide, pH=7) or to far above +320 mV (H₂O₂/HO^., H₂O pH=7) is essential for limitting Fenton reactivity. The oral chelating agents CP20, CP502, CP509, and ICL670 effectively remove iron from patients suffering from iron overload. We measured the electrode potentials of the iron(III) complexes of these drugs by cyclic voltammetry with a mercury electrode and determined the dependence on concentration, pH, and stoichiometry. The standard electrode potentials measured are ?620 mV, ?600 mV, ?535 mV, and ?535 mV with iron bound to CP20, ICL670, CP502, and CP509, respectively, but, at lower chelator concentrations, electrode potentials are significantly higher.     

Sensitive detection of cyclophosphamide using DNA-modified carbon paste, pencil graphite and hanging mercury drop electrodes

The interaction of cyclophosphamide (CP) with calf thymus double-stranded DNA (dsDNA) and thermally denatured single-stranded DNA (ssDNA) immobilized at the carbon paste (CPE) and pencil graphite electrodes (PGE), was studied electrochemically based on oxidation signals of guanine and adenine using differential pulse voltammetry (DPV).As a result of the interaction of CP with DNA, the voltammetric signals of guanine and adenine increased in the case of dsDNA while a slight increase was observed in ssDNA. The effect of experimental parameters such as the interaction time between CP and DNA forms and the concentration of CP, were studied using DPV with CPE and PGE. Additionally, reproducibility and detection limits were determined using both electrodes. A comparison of the analytical performance between CPE and PGE was done. Our results showed that these two different DNA biosensors could be used for the sensitive, rapid and cost effective detection of CP itself as well as of CP-DNA interaction.Furthermore, the interaction of CP with dsDNA and ssDNA was studied in solution and at the electrode surface by means of alternating current voltammetry (ACV) in 0.3 M NaCl and 50 mM sodium phosphate buffer (pH 8.5) supporting electrolyte, using a hanging mercury drop electrode (HMDE) as working electrode.The conclusions of this study were mainly based on tensammetric peaks I (at −1.183 V) and II (−1.419 V) of DNA. This study involved the interaction of CP with surface-confined and solution phase DNA where experimental parameters, such as the concentration of CP and the interaction time, were studied. By increasing the concentration of CP, an increase of peak II was observed in both ds and ssDNA, while an increase of peak I was observed only in the case of dsDNA. An overall conclusion of the study using HMDE was that the interaction of CP with surface-confined DNA significantly differed from that with solution phase DNA. The increase of peaks I and II was lower in the case of interaction of CP with surface-confined DNA, probably due to steric positioning of DNA at the electrode surface.     

Effect of phase behavior and pressure on the constant-volume heat capacity and intermolecular interaction of CO2-ethanol and CO2-n-pentane mixtures in the critical region

Study on the properties of the fluids near the critical point of mixed systems is a key for the development of supercritical (SC) technology and for the further understanding of the features of supercritical fluids (SCFs). The constant-volume molar heat capacity (Cv) of a solution is directly related to the internal energy, intermolecular interaction, and the microstructure of the solution. In this work, the Cv of CO2-n-pentane and CO2-ethanol systems was determined at 308.15 K in different phase regions. This work focuses on how the properties of the mixtures change with pressure, composition, and the structure of the components near the critical point of the mixtures. It was found that at fixed composition, a maximum in Cv versus pressure curve exists (Cv(max)) that occurs at the pressure at which the isothermal compressibility (K(T)) is the largest. We deduced that breaking the "clusters" in the SC mixtures is an endothermic process. It is very interesting that Cv increases sharply as the pressure approaches the critical point (CP) or bubble point (BP), while Cv is nearly independent of pressure and composition at the pressures well above the CP or BP pressure, and that the Cv at CP or BP can be several times larger than that at the high pressures. It can be deduced that at fixed composition the degree of "clustering" changes significantly with pressure near the CP or BP, and is the largest at CP and BP.     

二氧化钛多孔薄膜对含氯苯酚的电助光催化降解

用涂膜法制备了具有多孔微结构的二氧化钛薄电极,以制得的电极为工作电极,建立了三电极的电助光催化体系。选择含氟苯酚（４－氯苯酚,２,４,６－三氯苯酚）作为降解对象,进行光催化研究。实验结果表明,外加电极偏压可抑制光生电子－空穴的复合,提高二氧化钛的光催化效率;光强越强,降解速度越快。     

Nanoporous platinum solid-state reference electrode with layer-by-layer polyelectrolyte junction for pH sensing chip

A novel solid-state reference electrode was developed by combining nanoporous Pt with polyelectrolyte junction. The polyelectrolyte junction was formed in the microchannel connecting the nanoporous Pt and the sample solution, and had layer-by-layer structure of oppositely charged polyelectrolytes. The layer-by-layer polyelectrolyte junction effectively blocked the mass transport of ions and maintains constant pH environments on the surface of the nanoporous Pt. The assembly of the polyelectrolyte junction and the nanoporous Pt, which produced reportedly a stable open-circuit potential in response to constant pH, exhibited outstanding performance as a solid-state reference electrode (e.g., excellent reproducibility of ±4 mV (n = 5), good long term stability of ±1 mV (for 50 h), and independence of solution environments like pH and ionic strength). A working principle of the solid-state reference electrode with layer-by-layer polyelectrolyte junction was suggested in terms of the roles of each layer and the effect of the neighboring layer. As a demonstrative application of the solid-state reference electrode, a miniaturized chip-type solid-state pH sensor comprised of two nanoporous Pt electrodes and a micro-patterned layer-by-layer polyelectrolyte junction was developed. The solid-state pH sensing chip showed reliable pH responses without liquid junction and successfully worked in a variety of buffers, beverages, and biological samples, showing its potential utility for practical applications. In addition, the solid-state pH sensing chip was integrated in a microfluidic system to be utilized for pH monitoring in microfluidic flow.     

V(IV)在不同电极上氧化还原动力学研究

分别以导电塑料集流板、石墨棒、铂片作工作电极,应用循环伏安法和稳态极化法研究V(IV)的阳极氧化动力学过程,计算V(IV)在不同材料电极上的反应动力学参数.结果表明,以导电塑料板作电极,硫酸氧钒有较宽的水稳定区,且析氧电位较高;在石墨电极上,V(V)/V(IV)的交换电流密度较大,表现出较好的可逆性;而在铂电极上,硫酸氧钒更易析氢.     

Development of pH measurement system for legal traceability of pH standard solutions

The best reproducible technology of pH measurement for precise pH buffer solutions regulated by Japanese Industrial Standards (JIS) was studied. A pH meter was devised with a high resolution of +/- 0.0001 pH. An 18-bit analog-to-digital converter is used, one-bit resolution corresponding to 0.0019 mV (ca. 0.000032 pH) against an input electrode potential +/- 500 mV. Digital data were treated smoothly for some types of noise, a reproducibility of +/- 0.0002 pH being obtained with a potentiometer. A flow cell was devised to attain temperature control within +/- 0.03 degrees C and air-tight measurement prevented contamination with carbon dioxide. Also, the flow cell has a structure such that potassium chloride (KCl) inner solution effused from a ceramic junction of the reference electrode designed so as not to touch the glass membrane. A combination pH electrode (a glass electrode and a reference electrode) was assembled to minimize the dead volume of sample solution. This highly sensitive pH measuring system, consisting of a pH meter, a flow cell, a combination pH electrode, a circulating water thermostat and a peristaltic pump, was used for the certification of pH standard solutions in Japanese metrological law. The performance of this system was within +/- 0.0006 pH reproducibility and 20-30 min response time (5 min within +/- 0.0002 pH) at a sample flow rate of 3 ml min (-1).     

Liquid membrane potentiometric sensor for determination of Fe3+ ion

Solution studies showed a selective interaction between the new synthesized ionophore, 2-[(thiophen-2-yl)methyleneamino]isoindoline-1,3-dione (TMID) and Fe(III) ion. Therefore, TMID was used as an iron selective ion-carrier in a plasticized liquid membrane sensor. The linear response range of the proposed electrode was 1.0 × 10^?6–1.0 × 10^?2 M. The Nernstian slope of 20.1 ± 0.3 mV/decade, and a detection limit of 5 × 10^?7 M was obtained. The sensor could be used in the pH range of 2.3–4.8, and the response time was about 10 s. The lifetime of the electrode was at least 7 weeks. The sensor accuracy was investigated in two ways: (i) with the potentiometric titration of a Fe³⁺ solution with EDTA and (ii) with Fe(III) monitoring in some cationic mixtures. Finally, the newly fabricated electrode was effectively applied as an indicator electrode for the direct Fe³⁺ determination in real samples.     

Comparison of a single-use pH test strip and a glass electrode for potentiometric titration

The potentiometric titration of a carbonate mixture or an acetate solution is a common experiment in analytical laboratories. Typically, a glass electrode combined with a calomel or Ag/AgCl reference electrode is used to locate the equivalence points in neutralization titrations. The dissociation constants of weak acids and bases can be calculated from the pH at the half-neutralization point. Recently, a new commercial product for measuring pH has been developed. This novel acid–base detection strip is a single-use sensor that requires neither storage in a preservation liquid nor calibration prior to use. This study examined its suitability for the continuous monitoring of pH changes in potentiometric titrations of carbonate mixtures, acetate solutions, or ammonia solutions. There were no significant differences in the concentrations of solutions tested using a glass electrode and a pH test strip. The pK_a, pK_b, and pH values determined using the two systems differed by less than 5%. The results confirmed that the pH strips are suitable for continuously monitoring pH changes during neutralization titrations. However, the strips can only be used once.