Amperometric complex-formation titrations with a dropping indium amalgam electrode in halide medium

The applicability of a dropping indium amalgam electrode for the determination of metal ions in the presence of large concentrations of halides by means of amperometric complex-formation titrations using normal pulse polarography has been investigated. Titrations appear to be possible in the presence of 4M potassium iodide, 1M potassium bromide and 1M potassium chloride.     

Amperometric complex-formation titrations at a dropping mercury electrode, employing normal pulse polarography

Selective determinations of several metal ions by means of amperometric complex-formation titrations employing normal pulse polarography with a DME appear to be possible. Concentrations down to 3 x 10(-7)M have been determined with adequate accuracy. In alkaline medium deaeration is necessary; in acidic medium it can be omitted.     

Anodic behaviour of a dropping lead amalgam electrode in halide medium in the presence of EDTA

The behaviour of the dropping lead amalgam electrode has been studied. Calculated and experimental current-voltage curves have been compared and an explanation has been given for the observed differences. Selective determination of metal ions appears to be possible in the presence of saturated chloride, 1M bromide and 10(-2)M iodide by means of amperometric complex-formation titrations using normal pulse polarography with the dropping lead amalgam electrode.     

Amperometric complex-formation titrations of traces of copper

Copper has been determined in the submicrogram range by means of a eomplexometric titration with triethylenetetramine (TRIEN), the end-point being detected by following the anodic wave of the chelating agent at a rotating mercury electrode. The influence of the presence of other metals has been investigated both from the theoretical and the experimental point of view. Because of its higher selectivity TRIEN is preferred to other reagents of the EDTA group. The results show that copper can be determined in the presence of large amounts of most other metals.     

Polarographic determination of glycine with a dropping copper amalgam electrode

The anodic oxidation of a dropping copper amalgam electrode in presence of dilute solutions of glycine in 0.50 M NaClO₄ has been studied. An anodic wave at ?0.28V (SCE) is observed, yielded by diffusion of glycinate anion in the solution towards the electrode surface. The wave-heights increase with the glycinate concentration (function of glycine concentration and pH value) until the anodic oxidation is controlled by the metal diffusion into mercury. The effect of pH is interpreted by attributing it to the depolarizer effects at glycinate anion even though the zwitterion is present in much larger concentrations. The applicability of anodic oxidation of a dropping copper amalgam electrode in the determination of glycine in the range of concentrations 10^?4–10^?2M with a rigorous control of pH (8.0<pH<10.5) is shown. The standard deviation of the proposed method is 4.1% and the minimum concentration determinable is in the 1×10^?4M range.     

The influence of halides on amperometric complex-formation titrations with the rotating mercury electrode

The interference of halides with complexometric titrations, indicated by means of the anodic wave of the ligand at a rotating mercury electrode, has been studied theoretically. The effect of halides strongly depends on the pH of the solution. In alkaline solutions there appears to be no interference by chloride at all. A critical value for the halide concentration can easily be found for any medium. The theoretical predictions have been verified experimentally.     

Amperometric titrations with rotated platinum electrode: Determination of hydrazine by potassium bromate

The reaction between hydrazine and potassium bromate is studied amperometrically at rotating platinum electrode. The bromate titration is performed at an applied e.m.f. of zero (versus S.C.E.) and in the presence of bromide and 1–5N sulfuric acid or 0.5–4N hydrochloric acid. Quantities ranging from 30 μg to 3 mg of hydrazine can be estimated accurately by this method. Determination of phenylhydrazine, Semicarbazide and other oxidizable materials on similar lines is suggested.     

Amperometric titrations with the help of selenites

Summary A new procedure for rapid amperometric titration of cobalt based on precipitation of cobalt as the normal selenite is described. Potassium chloride (0.1 M) containing 0.01% gelatin as the maximum suppressor has been used as the supporting electrolyte. The use of 50% overall concentration of methanol was found essential for these titrations. The concentration of alcohol necessary for cobalt concentrations below 2 millimolars was 70%. The titrations have been performed at an applied potential of –1.5 volts vs. S.C.E. Effect of methanol on the equivalence point of the titration has also been studied. The procedure described gives accurate results, which agree well with the formula CoSeO₃ for the normal selenite of cobalt.     

Extractive indicators in complex-formation titrations: theory and practice

The use of conditional constants to predict the optimum conditions for titration in several complex-formation titrations, in which the end-point is detected by the formation of a coloured extractable complex, is demonstrated. The predictions have been tested by experiment. 2-(2-Pyridylazo)-1-naphthol is shown to be a useful extractive indicator for the copper-EDTA titration; dimethylglyoxine is not recommended as an extractive indicator for the nickel-EDTA titration; the titration of fluoride with aluminium, using 8-hydroxy-quinoline as an extractive indicator, is shown to be undesirable theoretically and experimentally.     

Potentiometric titrations with a mercury-mercury sulphide electrode

Platinum foil coated with a film of mercury and mercury sulphide is recommended as electrode for potentiometric titrations with thioacetamide.     

Amperometric carbohydrate detection in flow systems by means of a bismuth modified platinum electrode

Bismuth modified platinum electrodes are used for constant-potential amperometric determination of carbohydrates in flow systems. The monitored response is stable and reproducible over more than two days. An attempt is made to gain more detailed information about the characteristics of the modified layer by electrochemical methods and X-ray photoelectron spectroscopy. The response proved to be linear over the investigated concentration range (1.1–1200 mol/L) and detection limits for glucose and fructose were found to be 1.1 mol/L.     

Potentiometric titrations of selenium with a fluoride-selective electrode

Selenite can be determined with a fluoride-selective electrode by two methods: a direct procedure based on the joint titration of selenite and standard fluoride with lanthanum and an indirect method based on precipitation of selenite with excess of lanthanum followed by back-titration with fluoride. In the first case the end-point is located by the second derivative method, and in the second case by means of a Gran plot. Direct titrations are suitable for selenite concentrations above 5 mM; indirect titrations are useful for concentrations as low as 0.5 mM.     

Adsorption of alkanes on a bismuth electrode from an alcoholic medium

The adsorption of higher alkanes (from C₁₀H₂₂ to C₂₁H₄₄) on a polarized bismuth electrode was studied from methanolic, ethanolic and n-butanolic solutions of LiClO₄ by differential capacity measurements. Alkane molecules, which do not contain either polar groups or double bonds, are compounds of low chemical activity. The adsorption of this group of compounds is purely physical. Nevertheless, a considerable difference in their adsorption activity on the various areas of the electrode surface caused by the two types of bond (metallic and covalent) between the atoms in the bismuth crystal lattice was discovered. Such a large difference indicates the different wettabilities of the separate single-crystal faces by alkanes. A weak dependence of the interaction parameter in the Frumkin isotherm on the length of the alkane molecule as well as on the length of the hydrocarbon chain of the solvent molecule was established. Various adsorption effects at high bulk concentrations of adsorbate (desolvation of the cations of the supporting electrolyte, thickening of the adsorption layer, maximum in the isotherm) were analysed.     

Polarographic determination of phenylalanine,tyrosine, methionine,glutamic acid and histidine with a dropping copper amalgam electrode

The anions of the phenylalanine, tyrosine, methionine and glutamic acid give an anodic wave when a dropping copper amalgam electrode is oxidized in their presence, approximately at the same half-wave potential of that of the glycine anion (?0.28 V vs. SCE). The height of these waves depends on pH and amino acid concentration and can be utilized for the polarographic determination of these substances using the same procedure as that described previously for the determination of glycine. The polarographic behaviour of histidine is somewhat different because the zwitterion of this amino acid reacts with the Cu²⁺ and the anion forms a more stable complex. The polarographic determination of histidine can be also carried out with the same procedure.     

Electrometric titrations with the gold electrode

Summary Massive gold because of the passivity of the oxide formed on its surface can be used as a substitute for platinum in electrometric titrations including acid-base and oxidation-reduction systems. The end points are attended with large jumps on the curves and coincide satisfactorily with those obtained using the hydrogen or platinum electrode or by other method.     

The use of the rotated dropping mercury electrode in polarographic analyses and amperometric titrations of micromolar solution

The applicability of the rotated dropping mercury electrode in conventional direct current polarography, alternate current polarography, and amperometric titrations, has been investigated. The direct current polarographic method was applied to the determination of minute quantities of lead contained in high-purity electrolytic zinc, the lowest content of lead determined being 0.0001 %. It was confirmed that the rotation of the electrode has no advantage in alternating current polarography. Some characteristics of the electrode, revealed by the measurement of current-time curves, are also presented and discussed.     

Amperometric measurements with ion-selective electrode membranes in a flow system

Calcium and salicylate sensitive electrode membranes based on plasticized PVC were used for selective amperometric detection in a flow injection system. The peak current was found to depend linearly on concentration and the working range extended well below the potentiometric detection limit.Dedicated to Professor W. Simon on the occasion of his 60th birthday