Uncertainty and other metrological parameters of peroxide value determination in vegetable oils

Measurement uncertainty in the proposed redox-potentiometric methods for peroxide value (PV) determination in vegetable oils is evaluated in comparison with uncertainty in the standard methods. The methods determine all peroxides in oils, in terms of milliequivalents per kg of sample (meq/kg), that oxidize potassium iodide (KI) under the conditions of the test. The standard methods are based on KI oxidation by the oil test portion and volumetric titration of the liberated iodine, while the proposed methods are using redox-potentiometric iodine determination without titration. As far as fresh refined oils have PV≤0.5 meq/kg, the limit of detection (LOD) and limit of quantitation (LOQ) of the methods are important. An approach to assess the LOD and LOQ using uncertainty calculation was applied. It is shown how important is the influence of the solvents purity on the values of LOD and LOQ. Received: 1 August 2001 Accepted: 20 October 2001     

Microiodométrie au spectrophotomètre. Application au microdosage des phosphites

The general procedure of micro-iodometry is described, which permits, by the addition of KI in acid medium, the augmenting of the stability and intensity of coloration of dilute aqueous solutions of iodine (1–10 γ/ml).The conditions of oxidation of HPO₃^-2 by iodine are set out and applied to a microdetermination of phosphites by spectrophotometric determination of excess iodine, after addition of KI.     

A rapid iodometric method for the determination of copper and zinc

A method has been described for the iodometric simultaneous determination of zinc and copper. Copper is determined in the presence of sufficient KCNS and a small amount of KI. This is followed by the titration of the iodine equivalent to the zinc, which is liberated by the addition of potassium ferricyanide solution.Interference is eliminated completely by keeping the solution neutral or just acid with phosphoric acid.Within the range under investgation, results are obtained which are accurate to ± 0.7%.     

Determination of oxygen in the new high-temperature superconductor HgBa2CuO4+x

The determination of oxygen in the superconductor HgBa₂CuO_4+x was carried out by dissolution of the sample in hydrochloric acid, addition of KI solution and thiosulphate titration of the iodine formed. Two versions of this procedure have been examined.     

Titrimetric microdetermination of uric acid and thioglycollic acid by amplification reactions

A simple amplification method for determination of 0.05-2 mg of uric acid or thioglycollic acid has been worked out. It depends on iodine oxidation of the uric acid or thioglycollic acid solutions, removal of the excess of iodine, oxidation of the resulting iodide with bromine, and iodometric titration of the resulting iodate. The coefficient of variation ranges from 0.7 to 2.4% for uric acid and from 0.5 to 1.9% for thioglycollic acid, depending on the amount of the acid.     

Micro and submicro iodometric determination of arsenite and sulphite ions by amplification reactions

Two methods are described for the micro and submicro iodometric determination of arsenite and sulphite ions involving 3- and 6-fold amplification reactions, respectively. The arsenite method is based on oxidation with an excess of periodate, masking of the unreacted periodate with molybdate, and final iodometric titration of the iodate released. The sulphite method depends upon oxidation with iodine and removal of its excess by extraction with chloroform, and oxidation of the iodide formed to iodate, which is determined iodometrically as usual. The two methods are simple, rapid, and accurate. The average recoveries obtained are 99.9 and 99.3% for arsenite and sulphite, respectively.     

Iodimetric determination of organolead compounds

A sensitive, rapid and accurate titrimetric method has been developed for the determination of 50-5000 mug of ethyl-lead or phenyl-lead compounds, based on their oxidation with a chloroform solution of iodine, removal of the excess of iodine, oxidation of the resulting iodide with bromine, and iodometric titration of the iodate formed. The coefficient of variation does not exceed 1.2% for amounts > 1000 mug of the organolead compound, but increases to 2.8% for the 50-mug level. The ethyl- and phenyl-lead compounds can be determined independently in mixtures.     

Titrimetric microdetermination of isoniazid by amplification reactions

An amplification method for the determination of (0.01–2.0 mg) isoniazid is described. It depends on oxidation of the isoniazid sample solution with a chloroform solution of iodine and removed of its excess, oxidation of the resulting iodide with bromine, and iodometric titration of the liberated iodate after 6-fold amplification. Alternatively, the liberated iodine is reduced to iodide, and again oxidized to yield 36 iodide ions for every iodide ion originally present. The coefficient of variation does not usually exceed 1.5% for above 0.5 mg of isoniazid but increases to 3.6% at the 0.01-mg level.     

New iodometric methods for the microdetermination of arsenic in organic compounds

New methods are described for the iodometric microdetermination of arsenic in organic compounds after wet digestion or oxygen flask combustion. After evaporation of the arsenic solution to dryness and dissolution of the residue in water, acetone is added and the solution is treated with iodide-iodate and the iodine liberated (by the interfering acids and the first dissociation step of arsenic acid) is reduced with thiosulphate. The KH(2)AsO(4) left is then reacted with zinc sulphate in presence of excess of KI and KIO(3). Acetone is added and the liberated iodine is titrated with thiosulphate. This titration corresponds to the second and third dissociation steps of arsenic acid and is used to calculate the arsenic content of the compound. When arsenicals not containing sulphur are decomposed by the oxygen flask method, the arsenic acid solution obtained is reacted directly with zinc sulphate in presence of KI and KIO(3) and the iodine released is titrated with thiosulphate. In this case, the titration corresponds to all three dissociation steps of arsenic acid. The average recoveries obtained by the two methods are 99.5 and 99.9%, respectively.     

Titrimetric microdetermination of salicylic, acetylsalicylic, and p-hydroxybenzoic acids by amplification reactions

A novel titrimetric method with amplification has been developed for the determination of 0.05–2.0 mg of salicylic, acetylsalicylic, or p-hydroxybenzoic acid. It depends on bromination of these compounds by bromine to tribromophenylhypobromite, which liberates iodine when treated with iodide. The liberated iodine is extracted with chloroform, reduced to iodide, oxidation of the resulting iodide with bromine, and iodometric titration of the iodate produced gives the sixfold amplification method. The coefficient of variation does not exceed 1% for above 0.5 mg of the studied compounds, but increases to 2.8% at the 0.05-mg level.     

Iodometric microdetermination of hydrazines by amplification reactions

Two new, simple, rapid, and accurate iodometric amplification methods are described for the micro and submicro determination of hydrazine. The first depends on oxidation with a chloroform solution of iodine and removal of its excess, oxidation of the resulting iodide with bromine, and iodometric titration of the liberated iodate. The second method is based on oxidation with periodate at pH 8, masking of the excess of periodate with molybdate at pH 3, and iodometric titration of the iodate. The order of amplification involved in the two methods is 6- and 3-fold, respectively. Micro amounts of hydrazine sulphate and dihydrochloride were determined satisfactorily by both methods, the average recoveries being 98.6 and 99.4%.     

Applications involving oxidation with ethanolic iodine. Rapid potentiometric method for some reductants

Rapid potentiometric method was adopted for the determination of small amounts of hexacyanoferrate(II), thiosulfate, thiocyanate, and ascorbic acid, based on oxidation with ethanolic iodine at different pH values and subsequently titration of iodide with mercury(II) using silver amalgam as indicator electrode. The potential breaks at the vicinity of the endpoints were sharp enough for their accurate detection. The method provides for accurate determination of small amounts of some reductants of analytical importance.     

Electrooxidation of iodide in the presence of 4-hydroxycoumarin: application to a simple coulometric titration of 4-hydroxycoumarin.

The electrochemical oxidation of iodide ion in the presence of 4-hydroxycoumarin (1) was studied using cyclic voltammetry and controlled-potential coulometry. The result indicates that the resulting iodine takes part in a halogenation reaction and reacts with 4-hydroxycoumarin (1). According to the obtained results, a new and simple coulometric titration method with potentiometric end-point detection for the determination of 4-hydroxycoumarin (1) is presented. In the presented method, 2-200 micromol of 4-hydroxycoumarin (1) was successfully determined.     

Determination of formates by oxidation with iodine

A selective determination of formates based on oxidation with iodine at 100° in presence of potassium hydrogen tartrate, and final titration with thiosulphate solution, is described. The error is below 0.5% for 25–90 mg of formic acid. Few other organic acids interfere.     

Iodometric microgram determination of Mn(II) in aqueous media by an indirect chemical amplification reaction

A rapid, simple and highly sensitive iodometric amplification method is described for the determination of microgram amounts of Mn(II). The method is based on oxidation of Mn(II) with an excess of periodate in acetate buffer (pH 2.8-3.0), masking of the unreacted periodate with molybdate, and after addition of iodide, titration of the liberated iodine is with thiosulphate. The proposed method offers 20-fold amplification for Mn(II) and was found suitable for the determination of Mn(II) in the presence of permanganate ions. Mn(II) in tap water and an industrial waste water has been successfully determined by the proposed method.     

Determination of oxygen in the new high-temperature superconductor HgBa2CuO4+x

The determination of oxygen in the superconductor HgBa₂CuO_4+x was carried out by dissolution of the sample in hydrochloric acid, addition of KI solution and thiosulphate titration of the iodine formed. Two versions of this procedure have been examined. Correspondence to: Dr. Scheurell, Institut für Anorganische Chemie, Humboldt-Universität, Hessische Strasse 1/2, D-10115 Berlin, Germany     

Simultaneous determination of both the calibration constant in an electrochemical quartz crystal microbalance and the active surface area of a polycrystalline gold electrode

A novel method is employed for the simultaneous determination of both the calibration constant of an electrochemical quartz crystal microbalance (EQCM) and the active surface area of a polycrystalline gold electrode. A gold electrode is immersed into a 1 mM KI/1 M H₂SO₄ solution and on which forms a neutral monolayer. The adsorbed iodine can then be completely oxidized into IO₃⁻. The active surface area of a gold electrode can be obtained from the net electrolytic charge of the oxidation process, and the calibration constant in the EQCM can be calculated from the corresponding frequency shift. The result shows that this method is simple, convenient and valid.     

Coulometric redox titrations of some biologically active thiols with iodine in methanol and bromine in acetic acid

The possibility of coulometric titrations of cysteine, 2-thio-uracil, 6-mercaptopurine, and 6-thioguanine with iodine and bromine in methanol and with bromine in acetic acid has been investigated. Conditions have been found for the direct titration of the test substances with iodine in methanol based on their 1-electron oxidation to the corresponding disulphides and for their direct and indirect determination with bromine in acetic acid based on their 6-electron oxidation to the corresponding sulphonic acids.On leave from Department of Analytical Chemistry, Charles University, Prague, Czechoslovakia     

Application of the Iodide Ion-Selective Electrode in the Potentiometric Determination of Chloral Hydrate

Abstract

A simple and sensitive micro method for chloral hydrate determination based on oxidation with iodine in chloroform solution is described. The produced iodide ion in the extract is determined using the iodide ion-selective electrode by either a direct measurement, standard addition technique or potentiometric titration with standard silver nitrate solution. Samples containing 0.1 - 4.0 mg chloral hydrate are analyzed with an average recovery of 99-9% and standard deviation of 0.1%.