The effect of platinum(IV) on the coulometric generation of tin(II)

The current efficiency of tin(II) generation has been measured for various electrolytes and electrodes. The best results (>99.9%) were obtained with the paraffin-impregnated graphite electrode in 2M CaCl(2) + 0.2M HCl + 0.2M SnCl(4). In titrations of platinum(IV) with electrogenerated tin(II) in an electrolyte containing chloride or bromide it was found that the presence of platinum(II) or (IV) interferes in the cathodic generation of tin(II). The platinum is reduced to the elemental state at the electrode and causes simultaneous generation of hydrogen which decreases the current efficiency. This effect is more pronounced in chloride media.     

Precise coulometric titration of precious metals-II. Determination of platinum(IV) with electrogenerated chlorocuprous ion in KClCuEDTA buffer medium

A method for the precise coulometric titration of platinum(IV) with electrogenerated chlorocuprous ion in KClCuEDTA buffer medium is described. From 2.7 to 18.7 mg of platinum in pure platinum and platinum alloy are determined with standard deviations of less than or equal to 0.034% using potentiometric end point detection. The method has good accuracy and precision, selectivity and rapidity.     

Galvanostatic Coulometric Determination of Salicylic Acid and Some of Its Derivatives Using Electrogenerated Halogens

Reactions of electrogenerated bromine and chlorine with salicylic acid and some of its derivatives were studied. Procedures for the galvanostatic coulometric determination of 2.4 to 19.2 g/mL of salicylic, acetylsalicylic, para-aminosalicylic acids and mesalazine in model solutions and medicinal preparations with electrogenerated halogens were developed (RSD varied from 1 to 5%). The end-point of coulometric titration was determined amperometrically with two polarized platinum electrodes.     

Electrogenerated bromine as a coulometric reagent for the estimation of the bioavailability of polyphenols

A method is proposed for the estimation of the bioavailability of polyphenols using electrogenerated bromine as a coulometric titrant. The titration of model solutions of casein and bovine serum albumin (BSA) shows that casein does not interact with electrogenerated bromine, while BSA reacts with the titrant in the ratio 1: 63. The proteins bind rutin and quercetin (from 14 to 90%) at a high rate and thus reduce the bioavailability of polyphenols. The concentration of free polyphenol is reduced with an increase in the concentration of protein in the mixture. The total antioxidant capacity (AOC) of tea is determined. Green tea is shown to possess higher AOC than the black one because of the partial oxidation of polyphenols to respective thearubigins and theaflavins at the fermentation step in the production of green tea. The total AOC of tea drops from 7 to 85%, in proportion to the increase in the amount of milk in the mixture. Milk proteins bind tea polyphenols into complexes because of intermolecular interactions and thus reduce their bioavailability. The observed effect of milk is independent of the brand of black tea. The degree of reduction of the total AOC of tea in going from one tea to another remains virtually constant.     

Thin-layer hydrodynamic biamperometric end-point detection: application to the coulometric titration of arsenic(III) with bromine

A sandwich-type thin-layer cell has been applied to hydrodynamic biamperometric end-point detection in coulometric titrations. The detector cell, constructed from two pieces of teflon, has platinum indicator electrodes and is placed in a flow loop attached to the coulometric titration cell. The thin-layer cavity has a volume of 6.5 μl and a thickness of 51μm, which are obtained using teflon tape as a spacer. A peristaltic pump maintains a continual flow through the loop. The titration cell is a closed vessel completely filled with the solution to be titrated. Operational amplifier circuits control the potential difference applied across the two thin-layer electrodes, and to measure the current developed in the thin-layer cell. Noise arising from the pulsed nature of the flow is reduced by a factor of 25 by using an electronic filter. The titration of arsenic(III) with electrogenerated bromine was used to study the performance of the system. Concentrations from 24 ppb to 1.6 ppm can be determined with relative inaccuracies of +4 and +0.1%, respectively.     

Determination of trace tin by stripping potentiostatic coulometry

On the basis of voltammetric and coulometric studies of the behavior of tin(II) in a 2 M HCl solution at a carbon-graphite bulky electrode made of fibrous porous felt (FPF), we have found the optimum conditions for the stripping potentiostatic coulometric determination of 10–1000 μg tin(II) by the reaction Sn(0)-ē ? Sn(I) after preconcentrating Sn(0) at the electrode surface. The relative standard deviation varied from 0.5 to 4%. The results of the coulometric determination of the number of electrons involved in the oxidation of Sn(0) suggest that the stripping Sn(0) from the surface of the FPF electrode proceeds in two stages. The first stage Sn(0) → Sn(I) was electrochemical, and the second stage Sn(I) → Sn(II) was chemical. The procedure was applied to the determination of ～1% tin in a jewelry alloy based on gold, silver, platinum, and copper.     

What is the weighing form in gravimetric determination of antimony(III) with oxine?

The gravimetric analysis of antimony(III) with oxine (8-quinolinol, Hox) was studied. The amount of antimony left in filtrate and washing solutions was corrected with the results of atomic absorption spectrometry. The weighing form, which had not been conclusive before the present study, was determined to be SbO(ox)(Hox)2. The result (purity of antimony(II) oxide: 99.84 +/- 0.05% (m/m)) of the gravimetric analysis was in good agreement with that of coulometric titration with electrogenerated iodine.     

Coulometric determination of sulfur-containing amino acids using halogens as oxidizing titrants

It is found that cysteine and methionine quantitatively react with electrogenerated halogens under the conditions of galvanostatic coulometry. Cysteine reacts with all titrants, and methionine reacts only with chlorine and bromine. The stoichiometric coefficients of reactions between cysteine and halogens are 1:3, 1:3, and 1:1 for chlorine, bromine, and iodine, respectively. These coefficients for methionine reactions with chlorine and bromine are 1:2 and 1:1, respectively. It is shown that cysteine can be selectively determined in its mixtures with methionine by coulometric titration with electrogenerated iodine. It is found that twofold amounts of methionine do not interfere with the determination of cysteine. A procedure is developed for the direct coulometric determination of methionine in tablets with a relative standard deviation of 3–5%.     

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.     

Determination of Uric Acid by Voltammetry and Coulometric Titration

Possible mechanisms of the electrochemical oxidation of uric acid at platinum, gold, graphite, and copper electrodes in a 0.5 M NaOH solution and phosphate (pH 6.86) and borate (pH 9.18) buffer solutions were considered. The stoichiometric coefficients in the reaction of boric acid with electrogenerated bromine and hypobromite ion were determined. Working conditions for the voltammetric determination of uric acid were selected and the detection limits for uric acid were found in model solutions and blood serum.     

Coulometric titrations of arsenic(III) and antimony(III) with electrically generated bromine in acetic acid

Conditions for the coulometric titrations were investigated. Arsenic(III) could be titrated by continuous or discontinuous generation of bromine, and antimony(III) by discontinuous generation or back-titration. The accuracy and reproducibility depend on the pretreatment of the platinum electrodes.     

Rearrangement of a (dithiolato)platinum(II) complex formed by reaction of cyclic disulfide 7,8-dithiabicyclo[4.2.1]nona-2,4-diene with a platinum(0) complex: oxidation of the rearranged (dithiolato)platinum(II) complex

Reaction of the title bicyclic disulfide 16 with [(Ph3P)2Pt(eta2-C2H4)] (2) yielded the corresponding (dithiolato)platinum(II) complex 17 by oxidative addition. The initial product 17 isomerized at room temperature in a [1,5]-sulfur rearrangement to give another (dithiolato)platinum(II) complex 18 in high isolated yield. Oxidation reactions of 18 with dimethyldioxirane (DMD) provided (sulfenato-thiolato)platinum(II) 23, (sulfinato-thiolato)platinum(II) 24, (sulfenato-sulfinato)platinum(II) 25, and (disulfinato)platinum(II) 26 complexes, the structures of which were elucidated by NMR spectroscopy and X-ray crystallography. The oxidation process took place regioselectively in the first step and chemoselectively in the second. The selectivities are discussed.     

Electrogeneration of gold(III) in halide media

Gold(III) was electrogenerated with high efficiency at constant current in halide media by oxidation of freshly electrodeposited gold on a platinum electrode. The electrolytes tested were 0.0005–1 M HCl, NaCl HBr, and NaBr. Potentiometric studies indicated that the tetrahaloaurate(III) complex was generated in each case with oxidation potentials ranging from 0.83 to 1.15 V. Arsenic(III) (20 μeq) was titrated potentiometrically in 0.1 M NaBr by using a gold indicating electrode; the efficiency was 99.90 ± 0.05%. Iron(II) was titrated in 0.01 M HCl to a biamperometric end-point with gold-plated platinum wire indicating electrodes polarized at 100 mV. Recoveries were 100.7± 1.8% (0.7 mg) and 100.4 ± 2.3% (0.4 mg). This new system allows titrations over a wide range of acidities and oxidation potentials.     

Coulometric Determination of the Antioxidant Capacity of Tea Extracts Using Electrogenerated Bromine

A coulometric procedure based on the reaction between aqueous extracts of tea with electrogenerated bromine compounds was proposed for the rapid estimation of the antioxidant capacity of different kinds of tea. The antioxidant properties of tea with respect to bromine are mainly due to naturally occurring flavonoids, tannins, and some vitamins. Photometric and coulometric data for black teas exhibit good correlation.     

Diastereoselective assembling of 21-C-alkylated nickel(II) complexes of inverted porphyrin on a platinum(II) template

Reaction of 21-C-methyl and 21-C-benzyl nickel(II) complexes of inverted meso-tetratolylporphyrin with platinum(II) dichloride or its bis(benzonitrile) complex yields a chloroplatinum(II) species containing two nickel(II) carbaporphyrinoids in a cis arrangement. One of the carbaporphyrinoids coordinates to the platinum ion with the external nitrogen while the other is bound with the external nitrogen and one ortho-carbon of the adjacent meso-aryl ring. The reaction is highly chemoselective. (1)H and (13)C NMR experiments in solution show the diastereoselectivity of the reaction. Single-crystal X-ray data confirm the presence of the diastereomer with opposite configurations of the Ni(II)-coordinated carbons in the subunits of the dimer. Cyclovoltammetric measurements reveal an anodic shift of the nickel(II) oxidation potentials of dimers with respect to those of the parent monomers and two different reduction couples. Reaction of unsubstituted inverted porphyrin with Pt(PhCN)(2)Cl(2) in chlorobenzene yields a monomeric platinum(II) complex of inverted porphyrin. This complex displays a markedly upfield (195)Pt NMR shift compared to tetraphenylporphyrinatoplatinum(II). Under strongly basic conditions deprotonation of the external nitrogen of inverted porphyrin and both electrochemical and chemical oxidation of platinum(II) center are observed.     

Coulometric determination of uranium with a platinum working electrode

Experimental conditions have been established which enable uranium to be determined coulometrically by the reduction of uranium(VI) to uranium(IV) at a platinum working electrode, by controlled-potential or controlled-potential-limit techniques. The procedure has been used successfully as a subsidiary method in the routine determination of uranium in pure uranyl nitrate solutions. The platinum electrode has several important practical advantages over the well established mercury-pool electrode for the coulometric determination of uranium. The consecutive determination of iron(III) and uranium(VI), or plutonium(IV) and uranium(VI) can be carried out with the same working electrode in the same solution and the coulometric oxidation of uranium(IV) to uranium(VT) is practicable. The rate of stirring of the cell liquor is much less critical in the case of the platinum electrode. Two main problems had to be overcome before a practical procedure could be achieved; hydrogen evolution during the uranium(VI)-(IV) reduction had to be eliminated so that 100% current efficiency could be obtained for the desired reaction and electrode-surface poisoning phenomena had to be controlled so that reaction times could be kept reasonably short. It was found that selection of a hydrochloric acid base solution containing a small amount of bismuth(III) enabled hydrogen evolution to be avoided: also electrode-surface poisoning with this base solution was not particularly serious and could be maintained at a satisfactorily low level by occasionally anodizing the electrode in dilute sulphuric acid. Bismuth(III) forms a complex with chloride ions and its presence increases the hydrogen overvoltage at the working electrode: no visible deposit of bismuth metal forms on the electrode during the uranium reduction. Samples containing nitrate can be analysed provided sulphamic acid is added to this hydrochoric acid base solution.     

Precise coulometric titration of precious metals III. Determination of gold (III) with electrogenerated chlorocuprous ion in KCl-Cu-EDTA buffer medium

A method for the precise coulometric titration of gold (III) with electrogenerated chlorocuprous ion in KCl-Cu-EDTA buffer medium is described. 7.45-16.8 mg of gold can be determined with potentiometric end-point detection (RSD = 0.04%). The method is applied to precise analysis of gold in pure gold, jewellery and gold alloys with good selectivity. The mechanism of electron exchange at the gold-plated platinum cathode-electrolyte interface during the process of titration and the reversibility of the electrode in the proposed electrolyte are discussed.     

The application of coulometry for total antioxidant capacity determination of human blood

New coulometric method for estimation of blood and plasma total antioxidant capacity (TAC) based on using electrogenerated bromine was proposed. TAC of blood from patients with chronic renal disease undergoing long-term hemodialysis was investigated. Statistical significant changes in TAC level of venous and arterial blood were found. Catalase activity and low density lipoproteins (LDL) concentrations were determined. Linear correlation between TAC and parameters mentioned was found. Contribution from some individual antioxidants was investigated. The developed method for TAC assay is expressive, simple, stable and reliable, and successfully could be used for TAC determination of some biological fluids. This method could be applied in clinic for estimation of blood TAC from patients.     

Voltammetric Determination of Tin(II) and Iron(II) on Mechanically Renewed Graphite Electrode in Tin-Plating Electrolyte

The analytical properties of the cathodic peak of tin(II) reduction and the anodic peak of iron(II) oxidation on a graphite electrode were studied with the electrode surface mechanically renewed directly in a solution before applying a potential in each measurement. The influence of the organic components of the phenolsulfonic tin-plating electrolyte on the cathodic current of tin(II) reduction and anodic current of iron(II) oxidation was studied. A dc voltammetric method was proposed for determining tin(II) directly in the phenolsulfonic tin-plating electrolyte, and iron(II) after the electrolyte is diluted tenfold with a 0.5M H₂SO₄ supporting solution.     

Cyclometallated platinum(II) complexes: oxidation to, and C-H activation by, platinum(IV)

A series of cyclometallated phenylpyridine platinum(II) complexes have been synthesised with a systematic variation in both the phenylpyridine and the ancillary ligand. Oxidation of one of the cyclometallated species leads to a number of isomeric platinum(IV) complexes, all of which eventually isomerize to a single compound. The route to these new compounds has been demonstrated to involve an initial slow oxidation followed by a rapid C-H activation to give doubly cyclometallated complexes. The solid state structures of a number of both the platinum(II) and the platinum(IV) species have been solved; many of the structures exhibited extended interactions that result in complex three dimensional packing.