Applications,involving the iodide ion: VIII. Direct and indirect determination of mercury(I) and analysis of mixtures. Analysis of chromium(VI)-chromium (III) mixtures. Determination of hypochlorite

Mercury(I), down to 3 ppm, has been accurately determined by direct titration with iodide or by back-titrating excess of iodide with mercury (II) using silver amalgam as the indicator electrode. The direct method and additional volumetric ones were applied to the rapid analysis of various mixtures involving mercury(I) with fair accuracy and precision. Analysis of Cr(VI)-Cr(III) mixtures involved potentiometric back-titration of excess iodide and of excess EDTA separately with mercury(II). Back-titration of excess iodide was successfully applied to the determination of hypochlorite.     

Reactions and properties of some trimethyleneplatinum(IV) complexes: X. Reaction with iodide and thiocyanate ions

The reaction between the platinacyclobutanes [$\text{PtX}{}_2\text{(CH}{}_2\text{CRR′C}$H₂)L₂] (X  Cl, Br; L  C₅H₅N, 4-CH₃C₅H₄N; R, R′  H, CH₃; R  H, R′  CH₃, C₆H₅) and iodide and thiocyanate ions in methyl cyanide solution has been studied. The C₃ moiety is eliminated as the cyclopropane and the process is first order with respect to the platinacyclobutanes and zero to half order with respect to the salt (MY). With the iodides the rate increases in the order Li < Na < K, Et₄N, and methyl substitution in the cyclobutane ring reduces the rate of reaction with Et₄NI. Added pyridine retards the reaction when L  C₅H₅N (X  Cl; R, R′  H) and added dimethylsulphoxide accelerates it.The mechanism suggested involves dissociation of an L ligand and attack of Y^? ions and of M⁺Y^? ion pairs on the five-coordinate intermediate formed.     

Extraction of trace amounts of cerium(III) by oxides of amines and its separation from cerium(IV)

The solvent extraction of cerium(III) from nitric, hydrochloric and sulphuric acid solutions by 4-(5-nonyl)pyridine oxide and trioctylamine oxide in xylene has been studied. The influence of the concentration of the solvents and salting-out agents is described. From the results of partition experiments attempts have been made to deduce the nature of the extracted species. The investigation shows that cerium(III) can be separated from cerium(IV) from very dilute solutions of mineral acids and also from moderate nitric acid media.     

Kinetic and mechanistic aspects of metal ion catalysis in cerium(IV) oxidation

This review discusses the kinetic aspects of different metal ion catalysis in Ce(IV) oxidation of different types of organic and inorganic substrates in aqueous acid media. The reactions have been categorised with the metal ions acting as the catalysts. The nature of mechanism of catalysis in Ce(IV) oxidation depends on the nature of substrate for a particular metal ion catalyst and it also largely depends on the nature of acid medium used. The utility and scope of the catalytic oxidation by Ce(IV) in analytical chemistry are discussed.     

Applications involving the iodide ion-X determination of copper and analysis of cation mixtures and alloys

A rapid, accurate and highly selective method has been developed for estimation of copper, based on separating it as the slightly soluble copper(I) iodide, and potentiometric back-titration of unreacted iodide, in the filtrate, with mercury(II). By its aid binary, ternary and quaternary mixtures as well as a variety of copper alloys have been successfully analysed.     

Reactions of pentaamminechloroplatinum(IV) with iodide and sulfite ions

The reactions of pentaamminechloroplatinum(IV) with potassium iodide and sodium sulfite are studied. In the presence of an equimolar amount of the iodide, the chloride ions are completely substituted without subsequent displacement of the ammonia molecules that are in the trans position to the entering iodide ions. The reaction with sodium sulfite is accompanied by the reduction of Pt(IV) to Pt(II). The reaction kinetics of pentaamminechloroplatinum(IV) with potassium iodide at 22, 40, and 50°C are studied. The rate constants and activation energy of this reaction are calculated.     

Complexation ion-exchange chromatography of some metal ions on papers impregnated with Ti(IV)-based inorganic ion exchangers

The chromatographic behavior of 40 metal ions is studied on titanium (IV) arsenate, titanium (IV) phosphate-, titanium (IV) molybdate-, titanium(IV) tungstate-, and titanium(IV) selenite-impregnated papers in 0.1M oxalic, citric, and tartaric acid as mobile phases. Similar studies are carried out on Whatman No. 1 papers for comparison. The ion-exchange capacity of these papers is determined, and their selectivity for different cations is discussed. The mechanism of migration is explained in terms of ion-exchange, precipitation, and adsorption. The prediction of elution sequence from RF values is also checked. The average Ri is found to be almost linearly dependent on the charge of the metal ions. The effect of the pKa of complexing acids on average RF values of 3d series metal ions is explained. A number of binary and ternary separations are achieved.     

Influence of some metal ions on the coprecipitation of Am(III) and Pu(IV) with BiPO4

The influence of increasing concentration of Na, Cs, Ca, Zn, Ni, Cr(III), La, Fe(III) and Al on coprecipitation of Am(III) and Pu(IV) with BiPO₄ has been studied. The coprecipitation of Am(III) decreases with increasing concentration of La, Fe(III) and Al and the coprecipitation of Pu(IV) decreases with increasing concentration of Cs, Fe(III) and Al. The other elements studied did not influence the coprecipitation of Am(III) and Pu(IV) with BiPO₄.     

Sequential titration of iron(II) and vanadium(IV) mixtures with cerium(IV) sulphate, with ferroins as indicators

The titration of vanadium(IV) with cerium(IV) sulphate, with nitroferroin as indicator, is proposed. Unlike ferroin, the indicator does not need a catalyst in this system. By suitable choice of experimental conditions iron(II) can be titrated first to a ferroin end-point and then vanadium(IV) to a nitroferroin end-point.     

Determination of cerium(III) and cerium(IV) in nanodisperse ceria by chemical methods

Percentages of different valence cerium species have been determined in powdery samples, redispersible compositions, and aqueous sols of nanodisperse ceria prepared from cerium(IV) and cerium(III) salts by various methods with or without organic stabilizers. Cerium(III) is shown to be virtually absent in nearly all of the CeO₂ samples studied. Organic stabilizers are shown to be capable of reducing cerium(IV) in aqueous CeO₂ sols.     

Co-catalysis by transition metal ions in the hydrogen ion catalysed oxidation of iodide ions. A kinetic study

The reaction between KI and [Fe(CN)₆]^3– ion, catalysed by hydrogen ions, was found to be catalysed further by PdCl₂. Separate reactions under similar conditions, studied in the absence as well as in the presence of PdCl₂ catalyst, were found to follow first order kinetics w.r. to [Fe(CN)₆]^3– and [H⁺], while the order was two w.r. to [I^–]. [Fe(CN)₆]^4– ions were found to have a negative effect while changes in ionic strength of the medium do not effect the reaction velocity. Reaction in the presence of PdCl₂ showed direct proportionality w.r. to [PdCl₂]. The rate and extent of the reaction, which takes place even at zero [PdCl₂] in the co-catalysed reaction, was calculated and was found to be in accordance with the rate values of the separately studied reaction at similar concentrations without adding PdCl₂.     

Complexing of cerium(IV) with nitrilotriacetic acid in the presence of sulfate and nitrate ions

Conclusions The authors have made a spectrophotometric investigation of the composition of the complexes formed in the system Ce(IV)-nitrilotriacetic acid in 1 M (NH₄)₂SO₄ and 1 M NH₄NO₃ solutions and have calculated the instability constants of CeX⁺ and CeX ₂ ^2– complexes.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1448–1451, July, 1976.     

Simultaneous spectrofluorimetric determination of cerium(III) and cerium(IV) by flow injection analysis

Cerium(III) (1–100 μg l^?1) is determined by injection into a carrier stream of hydrochloric, perchloric or sulphuric acid, and monitoring its native fluorescence. Cerium(IV) can be determined similarly by incorporating a zinc reductor minicolumn into the system. Splitting the injection sample so that only part passes through the reductor, and the remainder by-passes it, allows total cerium and cerium(III) to be detected from the two sequential fluorescence peaks obtained.     

Complexation of some phthalexons with metal ions: Determination of chromium and palladium

Conditions for the complexation of three new phthalexons with metal ions are studied. A selection of the qualitative and quantitative composition of a buffer solution is justified. Procedures are developed for the determination of chromium(III) and palladium(II) in industrial samples.     

Synthesis,composition and ion exchange properties of Sn(IV) and Cr(III) arsenophosphates: separation of metal ions

This paper deals with the synthesis of the arsenophosphates of various metals. The chemical composition, ion exchange capacity, thermal stability, concentration curves, elution curves, pH-titrations and IR studies have been performed on two materials, namely, Sn(IV) arsenophosphate and Cr(III) arsenophosphate. Their utility has been established by achieving four binary separations of industrial importance such as CuNi, FeCu, FeNi and CoNi on columns.     

Determination of gold(III) alone or in some mixtures and alloys by potentiometric titration of iodide

The present work is an application of iodide to the reduction of gold(III), in an attempt to develop new method for gold(III) based on potentiometric back-titration of the excess of iodide with mercury(II). Although it was proved by calculation that the reduction of tetrachloroaurate to the metal should proceed quantitatively to completion, yet our experiments showed that the reduction under ordinary conditions, gave Au(I) in the form of a white precipitate of AuI. We succeeded to push the reduction with iodide to the metal by an excess of ethanol-ether catalyzed iodide at somewhat elevated temperature.With the experimental conditions established a reliable procedure have been developed involving a potentiometric finish which enabled accurate determination of gold(III), either alone or in some of its alloys.     

Spectrophotometric determination of olanzapine by its oxidation with N-bromosuccinimide and cerium(IV)sulfate.

Three simple spectrophotometric methods have been described for the assay of olanzapine in its pure and pharmaceutical formulations. The direct method (A) is based on the drug oxidation with excess of N-bromosuccinimide in acidic medium and the two indirect methods (B and C) are based on the oxidation of the drug with excess of N-bromosuccinimide and cerium(IV)sulfate, followed by the reaction of the unconsumed oxidants with celestine blue. The calibration graphs were linear over the range 10 - 120 microg mL(-1) (method A), 0.5 - 6.0 microg mL(-1) (method B) and 0.6 - 3.0 microg mL(-1) (method C). After validation, the proposed methods were successfully applied to assay of olanzapine in its commercial tablets with mean percentage recoveries of 101.23 +/- 0.10, 96 +/- 0.10 and 94 +/- 0.04%. The mechanism of olanzapine oxidation with N-bromosuccinimide was also proposed.