p-Ethoxychrysoidine is studied as adsorption indicator in the direct titration of silver with iodide, bromide, thiocyanate and chloride at pH 4–5. The explanation given by Schulek and Pungor for the colour changes has been modified in the light of compound formation on the surface of the precipitate. The silver compound of p-ethoxychrysoidine has been isolated ; its behaviour provides a suitable explanation for the colour changes as well as the pH changes in the titrations. 相似文献
Ti/TiO2 indicator electrodes were prepared by plasma electrolytic oxidation (PEO) method in the tetraborate electrolyte and were used for potentiometric indication of chemical reactions of different types and for analysis of surface and industrial wastewaters on the example of potentiometric determination of alkalinity and chloride. The electrodes formed at current densities of 0.05, 0.1, 0.15 and 0.2 A/cm2 are different in composition, surface morphology and electroanalytical properties. The electrodes formed at a current density of 0.05 A/cm2 exhibit the highest pH-sensitivity and generate the highest analytical signal at the equivalence point in the acid–base and precipitation titrations. The maximum analytical signal at the equivalence point, exceeding in magnitude the analytical signal, obtained by classical Pt electrode in oxidation–reduction and complexometric titrations generates PEO layers formed at a current density of 0.05 A/cm2 and a platinum-modified nanoparticles. The results of the potentiometric titration of the surface and technogenic waters using as indicator Ti/TiO2 electrodes are comparable with the conventionally used glass electrode (to determine alkalinity) and Ag electrode (to the determine chloride) and the results of visual titration. The advantage of the obtained metal oxide systems is the ability to determine two hydrochemical parameters due to their multifunctionality and opportunity to work with a single electrode. In addition, these sensors offer some analytical characteristics such as sensitivity, good reproducibility, high mechanical stability and a simple preparation procedure. 相似文献
A titration apparatus plotting either the concentration of sample ion or the concentration of titrant ion has been tested. An antilog apparatus, converting measured e.m.f. values into concentrations is connected to ordinary titration equipment. The instrument has been tested by means of acid—base titrations (titrations of mixtures of weak acids and of a weak and a strong acid), precipitation titrations (determination of the chloride concentration in tap-water, titration of mixtures of halides), titrations with ion-selective electrodes (determination of the fluoride content of toothpaste) and complexometric titrations (determination of copper with EDTA, using mercuric ion as indicator ion and amalgamated silver rod as indicator electrode, or using a copper-selective indicator electrode). The method considerably simplifies the evaluation of the results as compared to conventional potentiometric titrations. 相似文献
Hydrophobized graphite electrodes activated with CuS/Ag2S can be used to measure silver ion activities as effectively as silver sulphide electrodes, whereas electrodes activatd with PbS/Ag2S or CdS/Ag2S are useless for this purpose. The CuS/Ag2S electrode is also suitable for use in potentiometric titrations involving species that are not contained in the sensing material, but are capable of producing precipitates with silver or sulphide ions. 相似文献
The characteristics of polymeric sulfur nitride, (SN)x, electrodes for the sensing of pH in aqueous acid—base systems is reported. The application of this new pH-sensor to titrations of both strong and weak acids with strong base is described. The (SN)x. electrode has significant advantages for titrations of weak acids (pKa ? 9) with a strong base, compared to the classical procedure with the glass electrode. Comparative titration curves and quantitative results for hydrochloric acid, perchloric acid, trifluoroacetic acid, boric acid, p-nitrophenol, resorcinol, glycine, phenol, acetic acid, benzoic acid and propanoic acid with glass electrode and (SN)x electrode are given. 相似文献
The lower levels of the potentiometric titration of chloride with silver ions were investigated. The titrant was 0.001 N acetonic silver perchlorate. The titration media were acetone and acetic anhydride:acetone (4:1). A silver sulfide ion-selective indicator electrode and a double-junction reference electrode were use to monitor emf's. This titration is limited only by the trace amounts of chloride in the reagents used. Satisfactory results and well-defined titration curves were obtained down to 7 μg of chloride per 50 ml of solution (0.2 μmol; 4 × 10?6N).A small polarization current can be used to enhance the potentiometric breaks of this titration. In an 80% methanolic medium with 0.001 N aqueous silver nitrate and a polarization current of ?0.4 μA, the lower practical limit of this titration was near 22.3 μg of chloride (1.26 × 10?5N). 相似文献
A multiparametric curve-fitting procedure is described for locating the equivalence point of a potentiometric titration and is applied to data obtained in titrations of acetate ion with hydrochloric acid over a wide range of concentrations (down to 6.5 · 10-5M acetate). It does not depend on the existence of a point of inflection on the titration curve, and therefore yields useful results in titrations of this very weak base at concentrations well below that at which the point of maximal slope disappears. Three parameters are involved: the concentration of the base being titrated, the concentration dissociation constant Ka of its conjugate acid in the medium employed, and the apparent activity coefficient yH+ of hydrogen ion in that medium, and all three of these must be evaluated when a new supporting electrolyte is employed. In 3.0 M potassium chloride at 24°, the apparent activity coefficient of hydrogen ion is 1.7460, and this value permits data obtained in titrations of other or unknown bases in this medium to be interpreted by two-parameter fits. The value of Ka for acetic acid in this medium is 1.3134 · 10-5M; by means of these two numerical values routine titrations of acetate in this medium can be interpreted by one-parameter fits. It is possible to locate the equivalence point with an accuracy and a precision that cannot be approached by other techniques and even to obtain useful and reliable results under conditions so unfavorable that other techniques fail completely. 相似文献
In this work the volumetric and coulometric titrations of some newly synthesized androstene steroidal compounds with pyridine ring are carried out. The titrations were followed potentiometrically at a small constant current using pairs of identical platinum or glassy carbon electrodes, both in presence of quinhydrone. As the titration reagent, in volumetric titrations served 0.01 mol dm?3 perchloric acid, and in coulometric titrations hydrogen ions were anodically generated in situ from quinhydrone at the platinum electrode. Sodium perchlorate served as the supporting electrolyte.Amounts of 1.18-5.35 mg of the investigated steroidal compounds were determined with a relative standard deviation less than 1.4% at volumetric and 1.2% at coulometric determinations. A negative influence of the supporting electrolyte on magnitude of the signal change in potentiometric determinations was observed. Glassy carbon electrodes are more advantageous over platinum ones.The achieved results are in good agreement with those of catalytic thermometric titrations. 相似文献
The acid—base equilibria in the mixed solvent, 80% dimethyl sulfoxide—water, have been investigated by potentiometric measurements with a glass—silver—silver chloride electrode couple. The response of the glass electrode is quick and reproducible over the whole pH scale. The autoprotolysis constant (itKSH) of the mixed solvent has been determined; the value obtained, pKSH = 18.40, agrees well with reported data. The pKa values of the following aliphatic monocarboxylic acids are reported: formic, acetic, propionic, n-butyric, iso-butyric, n-valeric, iso-valeric, capric, pentadecanoic, stearic, monochloroacetic. The mixed solvent offers better titration conditions than water for the determination of these acids. 相似文献
The hydrophobic dyes tetrabromophenolphthalein ethyl ester and 2,6-dichlorophenolindo-phenol are proposed as visual indicators for two-phase titrations. The aqueous phase is colourless throughout the titration and these indicators make it possible to detect the end-point of the titration by the colour of one or the other phase. The indicators allow the two-phase titration of the silver(I)-1,10-phenanthroline complex with tetraphenylborate and of pentachlorophenol with tetraphenylphosphonium chloride. 相似文献
The systematic titration error which is introduced by the intersection of tangents to hyperbolic titration curves is discussed for precipitation reactions. A simple expression for the systematic titration error is derived, and S/Cx2 is proposed as a measure of the sharpness of the titration curve. The effects of the conditional solubility product (S), the concentration of the unknown component (Cx), and the ranges used for the construction of the end-point, are considered. A graphical method is presented for the selection of pairs of ranges which result in small systematic titration errors. For equal values of S/Cx2 and 1/KCx, the optimum combinations of ranges are different for precipitation and complexation titrations. The differences are not large for values smaller than about 0.002. For titration curves with a reversed L-shape, the error is calculated when the end-point is constructed by the intersection of the tangent to the second branch of the curve with volume axis; in this case equal ranges result in the same titration error for equal values of S/Cx2 and 1/KCx. The systematic titration error is equal to -S/Cx2 when the tangent to the curve is taken at fa = 3.0. 相似文献
Differential potentiometric titrations with two different ion-selective indicator electrodes are described. Ion-selective electrodes for Cl-, Br-, I-, F-, S2-, as well as glass and silver billet electrodes were used. The method was tested in the determination of binary mixtures of halides (Cl-, Br-, I-, and F-) by titration with solutions of silver nitrate, alone and mixed with lanthanum or thorium nitrate as required. Various factors influencing the determination were investigated. Results of simultaneous determinations of mixtures were in good agreement with the results of separate determinations within certain concentration limits. The method was successfully applied to the determination of a four-component halide mixture. Titrations of mixtures of fluoride with thiocyanate or hexacyanoferrate(III), and some other possibilities, are also reported. 相似文献
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. 相似文献
Magnetic titrations using a new titration cell and procedure are described. The paramagnetism of a hexammine nickel nitrate solution decreases linearly upon the addition of cyanide up to the endpoint (complete formation of Ni(CN)42-) ; there is no evidence of the formation of intermediate complexes. Intermediate complexes are evident in the titrations of iron(II) with 1,10-phenanthroline and with 2,2'-bipyridyl; log K1 values, calculated from the magnetic data, are 6.0 and 5.0 respectively. 相似文献
Standard potentials EM0 at 25, 50 and 75°C of all-solid-state silver-silver chloride ring membrane electrodes (Schott) with pressed-in silver foil have been measured with respect to the Pt, H2 electrode by means of a cell without transference (see also [1]) applied earlier by Bates and Bower who measured standard potentials E0 of corresponding electrodes of the 2nd kind. The data evaluated by the extended Debye-Hückel theory can directly be compared with the reported 2nd kind electrode data. Identical thermodynamic behavior of both electrode types is observed; small differences (<1.5 mV) of standard potentials and their temperature dependence are discussed on the basis of different states of electrode materials orignating from different electrode preparation and are applied to calculate thermodynamic data of membrane electrodes referred to those of electrodes of the 2nd kind. The results and contradictory literature data are discussed. A brief characterization of membrane and 2nd kind electrodes is given. 相似文献
The various steps in the development of the polarovoltric method and its utilisation in an automatic titration apparatus employing 2 polarized platinum electrodes are described. The method is based on the use of 2 types of polarization relationships applied to different chemical systems. These relationships are of the type I = f(V) and V = f(U), where V is the potential measured at the electrodes and U the potential applied to the electrodes across a resistance R, and are obtained directly from 2 indicating electrodes without the need for a reference electrode.The advantage of these relationships over the classic I= f(E) curves, where E is the potential of the indicating electrode with respect to a reference electrode, is to facilitate the prediction of the titration curves as a function of the resistance R and the applied voltage U. The use of these relationships has shown that a fixed applied voltage U of 3 V and a fixed series resistance R of 0.5 megohm are the most suitable for a differential polarovoltmeter for semi-automatic titrations.A symbolic notation is described which indicates the origin of the observed variations in potential. This notation permits a simple interpretation of polarovoltric curves and the rational use of unsymmetrical electrode arrangements. 相似文献
In complexometric titrations various indicator electrodes may be employed for monitoring the course of titration and for detection of the end-point. Several of them, including the silver, mercury, bivalent cation membrane, calcium membrane and manganese dioxide electrodes were investigated and compared in their usefulness. As titrant, EDTA was mostly used, but results with similar chelating titrants were also obtained. The practical utility of the electrodes in titrations depends on their selectivity, magnitude of the end-point break and precision in determination of the end-point. For the electrodes studied, in some instances there is good correlation between the theoretical and experimental titration curves, but it is not always possible to predict the electrode response in the low activity range. In other cases poor correlation does not mean that reasonably good analytical results may not be obtained. 相似文献
A titrimetric determination of some sulphonamides with 0.1 M sodium hydroxide in the presence of hexadecylpyridinium chloride is described. Potentiometric titrations are slow; visual titrations are satisfactory. The pKa shift can be interpreted in the light of general micellar behaviour. 相似文献
Summary Conductometric titrations of thorium chloride against oxalic acid, ammonium oxalate and silver nitrate have been carried out at high dilutions (0.001, 0.0005 and 0.00033 M) of the chloride. Oxalic acid is found to be a suitable titrant for rapid estimation of thorium, the minimum error being +0.5%. The other titrants do not give good results. The titrations with ammonium oxalate indicate the step-wise ionisation of ThCl4 into ThCl22+, ThCl3+ and Th4+. For mixtures of thorium chloride and cerous chloride, only the equivalence point corresponding to complete precipitation of both thorium and cerium is indicated.The authors express their sincere thanks to Prof. S. S.Joshi for his keen interest in this work and to Dr. G. S.Deshmukh for his advice and help in so many ways during the progress of these studies. 相似文献
Many solid-state electrodes were found to respond as endpoint detectors in the potentiometric titration of large inorganic and organic anions with quaternary ammonium halides. The best response was obtained with the iodide and cyanide electrodes although practically any electrode can function as endpoint sensor. The titrants were hexadecylpyridinium chloride and hexadecyltrimethylammonium chloride; hexadecyltrimethylammonium bromide and Hyamine 1622 may also be used. Some inorganic anions thus titratable are perrhenate, persulfate, ferricyanide, hexafluorophosphate, and hexachloroplatinate. Examples of organic anions titratable are nitroform, tetraphenylborate, cyanotriphenylborate, picrate, long-chain sulfates and sulfonates, and some soaps. The reverse titration of quaternary ammonium halides vs dodecylsulfate is also feasible. Some titrations are feasible in a partially nonaqueous medium. 相似文献