Electrolytically generated silver(II) as a coulometric titrant

The use of electrolytically generated silver(II) as a coulometric titrant has been studied. Difficulties arising from the current efficiency for generation of silver (II) at a platinum or gold electrode and from the reduction of silver(II) by water, have been overcome. The precautions necessary for accurate titrations of oxalic acid, cerium(III), arsenic(III) and vanadium(IV) by amperometric or potentiometric methods are detailed. Manganese and chromium could not be determined directly. Substances which reduce nitric acid could be determined if care was taken.     

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.     

Comparison of the adsorption orientation for 2-mercaptobenzothiazole and 2-mercaptobenzoxazole by SERS spectroscopy

In this study, the adsorption orientation for 2-mercaptobenzothiazole (MBT) and 2-mercaptobenzoxazole (MBO) on to silver mirror and silver sol substrates have been studied by surface enhanced Raman scattering (SERS). The MBT and MBO were chemisorbed on both silver mirror and silver sol after deprotonation with a tilted orientation to the silver surfaces. The surface enhanced properties of MBT and MBO showed that the substrate of silver mirror was superior to the sliver sol. The SERS spectra of MBT and MBO revealed that both of the MBT and MBO were adsorbed on silver surfaces strongly by a common sulfur molecule and a sulfur atom from MBT and an oxygen atom from MBO. Therefore, the adsorption orientation of MBT and MBO was little tilted perpendicularly to the silver surfaces. The adsorption geometry did not undergo any significant changes in acidic and basic solutions. It showed that the adsorption orientation for MBT and MBO were stable in the both solutions.     

One-pot electrosynthesis of polyglycine-like thin film on platinum electrodes as transducer for solid state pH measurements

The anodic oxidation of concentrated glycine based aqueous electrolyte on smooth platinum electrode leads to a strongly grafted polyglycine-like coating on the surface in an irreversible way. Due to the proton affinity towards amino groups of polyglycine (PG), the electrodeposited thin film was used as receptor for solid potentiometric pH sensor. In order to reach local pH measurement, we developed miniaturized microelectrodes on glass substrate thanks to photolithography process. We used silver chloride on silver as the reference electrode. The couple (silver chloride, PG based platinum electrode) of microelectrodes gives linear potentiometric response vs. pH in the range [2-12], reversibly and with a sensitivity of 52.4 mV/pH (for 1 mm electrode size). PG based pH electrode is compared to other organic polymer based pH receptor such as linear polyethylenimine (L-PEI), polyaniline (PANI) and glass membrane.     

A self-generating third-order electrode: Part II. Analytical applications of the silver—silver sulphide electrode

Analytical applications of the silver—silver sulphide electrode are illustrated by potentiometric determinations of Cd(II) and Pb(II) ions. The stability of the electrode potential in the presence of oxidizing agents is demonstrated by various titrations with silver(I) solutions. The influence of pH on the electrode potential in pure acidic solutions is noted. The electrode used was prepared by electrolytic deposition of silver sulphide on a silver rod; after 2 years, it remained reliable, and was unaffected by light under normal laboratory conditions.     

Amperometric and constant-current potentiometric determinations of the Landolt effect

An amperometric method with one platinum indicator electrode as well as the constant-current potentiometric method with one and two indicator electrodes were successfully applied to the Landolt effect determination by means of the hydrogen peroxide-iodideascorbic acid and bromate-bromide-ascorbic acid indicator reactions. The possibilities of application of these methods are illustrated by the determination of small amounts of iron(III), vanadium(V), and molybdenum(VI) with satisfactory accuracy and precision.     

Voltammetric behavior of the iron(II)-(III) and cerium(III)-(IV) couples in potentiometric titrations at constant current and amperometric titrations with two indicator electrodes

The voltammetric behavior at the rotated platinum electrode of the iron(II)-(lII) and cerium (III)-(IV) couples in sulfuric and hydrochloric acids has been investigated The iron and cerium couples are not reversible at a platinum electrode when current flows in the system, and the current-potential curves deviate considerably from those predicted on the basis of reversibility Titration curves for potentiometric titrations at constant current using one and two indicator electrodes are predicted from the current-potential curves and compared with the experimental curves.The degree of reversibility of the iron couple depends greatly on the pretreatment of the electrode The current-potential curves of the iron couple at a platinum electrode coated with a monomolecular film of platinum oxide approach reversibility while those at a clean electrode are highly irreversible Experimental and calculated titration lines for amperometric titrations using two indicator electrodes are compared, and the effects of medium and applied e.m.f. upon the characteristics of the titration curves are considered.     

Selectivity coefficients for amperometric sensors

Selectivity coefficients (k(amp)(ij)) are introduced as well-defined measures of the selectivity of amperometric sensors. For any amperometric device the total current response in the presence of interfering species (j) can be described by the general equation; i(t) = K(C(i) + Sigmak(amp)(ij)C(j)), where i is the target analyte. Equations are derived for k(amp)(ij) under different conditions common in amperometric sensing. Factors influencing the selectivity coefficients of amperometric probes, including the recognition and transduction mechanisms, the controlled-potential operating technique, and the transducer geometry are discussed. The selectivity coefficient strategy is illustrated experimentally with two widely used applications of amperometric devices, the anodic monitoring of dopamine at Nafion-coated electrodes and the biosensing of glucose at glucose-oxidase enzyme probes. It is anticipated that the selectivity coefficient strategy will become widespread in amperometric devices, and for chemical sensors in general, and will not be limited only to potentiometric probes.     

Photolithographically patterned enzyme membranes for the detection of pesticides and copper(II) based on enzyme inhibition

Summary A non-aqueous and an aqueous photopolymer system with an enzyme are used to prepare photolithographically patterned enzyme membranes for amperometric (thinfilm platinum electrode) and potentiometric (ISFET) sensors based on enzyme inhibition. Flow methods for enzyme inhibition tests are described. The decrease in enzyme (AChE) activity after incubation in a solution of dichlorvos as inhibitor is detected amperometrically. The enzyme urease is immobilized onto the pH-sensitive gate area of an ISFET. Such a biosensor is able to detect copper-(II) in water in the ppm-range without preconcentration.Dedicated to Professor Dr. Wilhelm Fresenius on the occasion of his 80th birthday     

Potentiometric Immunosensor Based on Immobilization of Hepatitis B Surface Antibody on Platinum Electrode Modified Silver Colloids and Polyvinyl Butyral as Matrixes

A highly sensitive immunosensor based on immobilization of hepatitis B surface antibody (HBsAb) on platinum electrode (Pt) modified silver colloids and polyvinyl butyral (PVB) as matrixes has been developed for potentiometric immunoanalysis to detect hepatitis B surface antigen (HBsAg) in this study. HBsAb molecules were immobilized successfully on nanometer‐sized silver colloid particles associated with polyvinyl butyral on a platinum electrode surface. The modification procedure was electrochemically monitored by electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The HBsAb‐silver‐PVB‐modified electrode exhibited direct electrochemical behavior toward HBsAg. The factors influencing the performance of the resulting immunosensor were studied in detail. More than 94.7% of the results of human serum samples obtained by this method were in agreement with those obtained by enzyme‐linked immunosorbent assays (ELISAs). The resulting immunosensor exhibited a sigmoid curve with log HBsAg concentration, high sensitivity (39.8 mV/decade), wide linear range from 16.0 to 800 ng mL^?1 with a detection limit of 3.6 ng mL^?1, fast potentiometric response (<3 min) and long‐term stability (>4 months). The response mechanism of the immunosensors was also studied with AC impedance techniques.     

Amperometric titration of palladium, silver and copper with benzimidazol-2-ylmethanethiol, and its application to non-ferrous materials

A method is described for the determination of mg amounts of palladium, silver and copper by amperometric titration with benzimidazol-2-ylmethanethiol in acetate buifer medium (pH 4-5) at an applied potential of -0.2 V vs. the saturated calomel electrode. Direct titrations are possible in the presence of a number of foreign ions. Copper and palladium interfere mutually and in the determination of silver. Mercury(I), mercury(II) and platinum(IV) also interfere. Silver does not interfere in the determination of copper and palladium if it is first precipitated as chloride. The method has been successfully applied to the analysis of non-ferrous materials.     

Kinetic determination of silver ion by its perturbation on Belousov-Zhabotinskii oscillating chemical reaction using potentiometric method.

Silver ion can perturb the Belousov-Zhabotinskii (B-Z) oscillating chemical reaction. Therefore, the B-Z oscillating system was applied in the determination of silver ion by using a platinum wire as an indicator electrode in the potentiometric method. The amplitude of the potentiometric oscillation increased linearly in proportion to [Ag+] in the range of 9.42 x 10(-6) M to 2.54 x 10(-4) M, with a correlation coefficient of 0.999 under the optimum conditions. The obtained LOD (2sigma) was 8.85 x 10(-6) M and the relative standard deviation (RSD) for five measurements of 1 x 10(-4) M silver ion was 5%. The influence of some potentially interference was also investigated.     

Direct Spectrophotometric Determination of Calcium in Human Serum and Cerebrospinal Fluids with Amino G Acid Chlorophosphonazo

ABSTRACT

A novel spectrophotometric method based on amino G acid chlorophosphonazo (AGCPA) has been developed for measuring calcium in human serum and cerebrospinal fluids. The effects of experimental factors including pH, reagent concentrations, and interfering species on calcium determinations were investigated. In a neutral reaction media of pH 7.0, AGCPA reacts rapidly with calcium to form a stable and greenish blue complex, whose absorption maximum is at 670 nm. The molar absorptivity (?) of the complex is 7.2x10⁴ 1 mol^?1cm^?1, and the molar ratio of calcium to AGCPA in the complex is found to be 1:2. Beer's law is obeyed over the range 0.02-0.8 μg ml^?1 of calcium. No interferences were observed from the commonly coexisting species present in serum and cerebrospinal fluids. Compared to the reported and currently often used methods based on o-cresolphthalein complexone, arsenazo III and methylthymol blue, the proposed method in this work provides better analytical characteristics such as high sensitivity, good selectivity and neutral reaction media. In addition, the present method is simple and can be applied to the direct determination of calcium in human serum and cerebrospinal fluid samples with satisfactory results.     

Étude polarographique du mercure (Hg+2) en présence d'acide éthylènediaminotétracétique: Titrage ampérométrique des cations par le complexon,basé sur la vague de dépolarisation anodique

The anodic depolarization wave of Hg⁺² by complexone (ethylenediaminotetraacetic acid) has been found to be proportional to the concentration of complexone (10^-4 to 10^-3 mole/liter, pH =6.4 in buffered medium). Titrationc of complexone by Mn⁺², Co⁺², Ni⁺², Cd⁺², Mg⁺², Zn⁺² gave, at the same pH of 6.4, normal amperometric curves. On the other hand, alkaline-earth cations, the complexes of which are less stable than the aforementioned ones, gave abnormal amperometric curves in that the height of the wave observed during titration is much larger than the one corresponding to the concentration of the complexone that is not involved in the formation of the complex.These results can nevertheless be interpreted in a satisfactory way by assuming that the measured current is determined on the one hand by diffusion and on the other hand by the rate of dissociation of the complexes in the vicinity of the electrode. The rate constant is greater the less stable the complex.     

Electrochemical detection coupled with high-performance liquid chromatography in pharmaceutical and biomedical analysis: a mini review

Recent advances in electrochemical detection techniques coupled with high-performance liquid chromatography (HPLC-ECD) in pharmaceutical and biomedical analysis are reviewed. ECD classification and modes including common amperometric, coulometric, conductimetric, and potentiometric detector, are outlined and the some typical examples of determinations in pharmaceutical and biomedical analysis are described. The electrochemical detection system can offer superior merits over other detectors commonly used with HPLC. These techniques have great potential owing to their prominent characteristics in high-throughput screening procedures of drugs in various matrices. Fundamental 67 references from last 5 years related with a field are cited in this review.     

表面吸附质对银亚胶体吸光特性的影响

纯银溶胶在390nm处有一吸收峰。当银溶胶吸附了1-苯基-5-巯基四氮唑(PMT)或2-巯基苯骈噻唑(MBT)时, 银溶胶由亮黄色转变为橙红色, 即在510～550nm处出现一个新的吸收峰。研究发现, 卤素离子在银溶胶颗粒上与PMT和MBT有竞争吸附作用。但是卤离子对银溶胶的光谱吸收的影响完全不同于PMT和MBT。在讨论这种差别时应首先考虑金属银溶胶颗粒表面性质因吸附不同物质所产生的变化。     

Evaluation of the potentiometric detection of acetylcholine and other neurotransmitters in capillary electrophoresis

It is demonstrated that acetylcholine may be determined potentiometrically in capillary electrophoresis down to 6 x 10(-7) M with a miniature coated-wire ion selective electrode. The more established amperometric method is not possible for this compound. Similarly, 4-aminobutyric acid (GABA) is not accessible amperometrically; although potentiometric detection was possible, the sensitivity is not good. Other neurotransmitters may be determined by either method, but in these cases amperometric determination is generally favorable. For serotonin the potentiometric detection limit was 4 x 10(-5) M, while for the amperometric method a detection limit of 10(-7) M was found.     

Conductometric titration of thiosulfate using new-type conductivity cells

The conductometric titration of thiosulfate with silver ions using non-conventional conductivity cells is described. For this purpose conductivity cells with different cell constants and electrode constructions, equipped with silver, amalgamated silver, stainless-steel and polished platinum electrodes were used. Two well-resolved break-points were observed at 1:1 and 2:1 silver/thiosulfate stoichiometries. Accurate conductometric determinations can be made, using the second break-points of the titration curves as equivalence points, in the range of thiosulfate concentrations 10(-4)-10(-2) M. Reverse titrations are less accurate.     

Comparison between amperometric and true potentiometric end-point detection in the determination of water by the Karl Fischer method

A rapid and sensitive method using true potentiometric end-point detection has been developed and compared with the conventional amperometric method for Karl Fischer determination of water. The effect of the sulphur dioxide concentration on the shape of the titration curve is shown. By using kinetic data it was possible to calculate the course of titrations and make comparisons with those found experimentally. The results prove that the main reaction is the slow step, both in the amperometric and the potentiometric method. Results obtained in the standardization of the Karl Fischer reagent showed that the potentiometric method, including titration to a preselected potential, gave a standard deviation of 0.001(1) mg of water per ml, the amperometric method using extrapolation 0.002(4) mg of water per ml and the amperometric titration to a pre-selected diffusion current 0.004(7) mg of water per ml. Theories and results dealing with dilution effects are presented. The time of analysis was 1-1.5 min for the potentiometric and 4-5 min for the amperometric method using extrapolation.     

Comments on the potentiometric titration of halides including fluoride with a mixed titrant

An attempt was made to verify work reported by others on the potentiometric titration of halides including fluoride with a mixed titrant of silver nitrate and thorium nitrate. The platinum indicator electrode can indeed be used to monitor the titration of bromide and chloride. However, we could not verify the results reported for fluoride. There seems to be no theoretical basis on which to expect the platinum electrode to respond to changes in fluoride ion concentration.