Sodium chlorite–iodine–methyl acetoacetate oscillatory reaction investigated by UV–vis spectrophotometric method

A new sodium chlorite–iodine–methyl acetoacetate chemical oscillatory reaction was studied using UV–vis spectrophotometric method. The initial concentrations of methyl acetoacetate, sodium chlorite, iodine, sulfuric acid, and the pH value have great influence on the oscillation observed at wavelength of 585 nm. There is a pre-oscillatory or induction period; the amplitude and the number of oscillations are associated with the initial concentration of reactants. The equations for the I₃ ^?–starch complex reaction rate changing with reaction time and the initial concentrations in the oscillation stage were obtained. The time of induction period decreases with the initial concentration of methyl acetoacetate or sulfuric acid, and increases with the initial concentration of sodium chlorite. A good linear relationship exists. Oscillatory reaction can be accelerated by increasing temperature. The apparent activation energies in terms of the induction period and the oscillation period were 114.28 and 64.92 kJ/mol, respectively. It may indicate that the two stages have different reaction mechanisms. The reaction of producing enol isomer by keto-enol tautomerism is an important step to constrain the time of induction period.     

Determination of low concentrations of chlorite and chlorate ions by using a flow-injection system

A flow-injection method is reported for the determination of chlorite ion and chlorite and chlorate ions in mixtures at the submilligram per liter level in drinking water. The chlorite ion concentration is selectively determined by using its reaction with iodide ion at pH 2, which liberates iodine. Both species react with iodide ion in6 M HCl to produce iodine, the concentration of which is measured spectrophotmetricaly at 370 nm. The individual species are determined using multiplel regression. The method exhibits a linear range from 2 to 150 μM (0.1–10.1 mg l^-1) for chlorite ion and from 2 to μM (0.1–8.3 mg l^-1 for chlorate ion, with relative standard deviations of 0.4 and 1.2%, respectively.     

Catalytic determination of molybdenum(VI) by means of an iodide ion-selective electrode and a landolt-type hydrogen peroxide-iodide reaction

A trace amount of molybdenum(VI) can be determined by using its catalytic effect on the oxidation of iodide to iodine by hydrogen peroxide in acidic medium. Addition of ascorbic acid added to the reaction mixture produces the Landolt effect, i.e., the iodine produced by the indicator reaction is reduced immediately by the ascorbic add. Hence the concentration of iodide begins to decrease once all the ascorbic acid has been consumed. The induction period is measured by monitoring the concentration of iodide ion with an iodide ion-selective electrode. The reciprocal of the induction period varies linearly with the concentration of molybdenum(VI). The most suitable pH and concentrations of hydrogen peroxide and potassium iodide are found to be 1.5, 5 and 10mM, respectively. An appropriate amount of ascorbic acid is added to the reaction mixture according to the concentration of molybdenum(VI) in the sample solution. A calibration graph with good proportionality is obtained for the molybdenum(VI) concentration range from 0.1 to 160 μM. Iron(III), vanadium(IV), zirconium(IV), tungsten(VI), copper(II) and chromium(VI) interfere, but iron(III) and copper(II) can be masked with EDTA.     

Simultaneous flow-injection measurement of hydroxide, chloride, hypochlorite and chlorate in Chlor-alkali cell effluents

A flow injection method is reported for the simultaneous determination of hydroxide, chloride, hypochlorite, and chlorate ions that exist in Chlor-alkali cell effluents in concentrations ranging from sub-millimolar to several molar. The hydroxide concentration is determined by the heat of neutralization of the injected sample into an acidic carrier stream and the chloride concentration is calculated from the measured conductance data. For the measurement of hypochlorite and chlorate, colorimetric iodometry is used. Iodide is oxidized to iodine by OCl(-) and ClO(3)(-) in acid solutions. While room temperature is sufficient for the reaction between OCl(-) and I(-), the reaction between ClO(3)(-) and I(-) requires an elevated temperature. The different reaction requirements are utilized to differentiate between NaOCl and NaClO(3), respectively.     

Chemical clock reactions: The effect of precursor consumption

During a clock reaction an initial induction period is observed before a significant change in concentration of one of the chemical species occurs. In this study we develop the results of Billingham and Needham (1993) who studied a particular class of inhibited autocatalytic clock reactions. We obtain modified expressions for the length of the induction period and show that characteristic clock reaction behaviour is only observed within certain parameter limits. This revised version was published online in July 2006 with corrections to the Cover Date.     

Kinetics and mechanism of the reaction between thiourea and iodate in unbuffered medium

The significances of thiourea and its derivativesnow spill into nonlinear dynamics in chemistry. A re-markable variety of complex dynamical phenomena,including oscillation, oligooscillation, variable stoichio-metries, autoinhibition, autocatalysis, bistability andbirhythmicity, traveling wave and chemical chaos,have been known in thiourea-based reaction systemsfor some time[1—7]. Also, a series of researches on thekinetics and mechanisms of the oxidations of thiourea,thiourea derivatives and …     

Removal of Ascorbic Acid Interference in Horseradish Peroxidase Estimations of Hydrogen Peroxide

Abstract

Ascorbic acid, which depresses the colour and interferes in reactions in colorimetric and fluorometric assay procedures for hydrogen peroxide involving horseradish peroxidase, has been removed from solutions by treatment with an iodine reagent. This reagent strongly interferes with procedures involving scopoletin, 2,2′-azinobis-(3-ethylbenzthiazoline-6-sulphonic acid) and the reaction between 3-dimethylaminobenzoic acid and 3-methyl-2-benzothiazolinone hydrazone. The iodine reagent slightly depressed the fluorescence obtained using hydroxyphenylacetic acid but this was the most suitable electron donor for amounts of hydrogen peroxide between 6 and 60 nmol. Hydroxyphenylacetic acid spontaneously reduces residual iodine.     

Alternating current polarographic determination of microgram amounts of iodide ion by means of the catalytic oxidation of 1-amino-2-naphthol-4-sulfonic acid

The catalytic oxidation of 1-amino-2-naphthol-4-sulfonic, acid proceeds quickly with microgram amounts of iodide in the presence of sodium chlorate at pH between 1.3 and 2.0. The oxidation product shows a sensitive tensammetric wave at potentials of about +0.03 V vs. SCE (pH 1.75), so that the catalytic reaction was applied for the determination of microgram amounts of iodide ion. The most suitable conditions of the pH range, the concentration of ANS and sodium chlorate, reaction temperature and standing are 1.3–2.0, 3 × 10^?4M, 0.05 M, 50° C and 1 h respectively. Using the recommended procedure, iodide ion can be determined precisely in the concentration range 0.4–6.5 ng ml^?1 with a relative error of about 3%. Interference of foreign species and the application to the determination of total iodine in river and sea water are described.     

Reaction of 2,3-Dimethylmercaptopropionic Acid with Methylene Blue as an Indicator Reaction for the Kinetic Determination of Selenium

A new indicator reaction between 2,3-dimethylmercaptopropionic acid and Methyl Blue was proposed for the kinetic determination of selenium. The optimal reaction conditions were found. A linear relationship was observed between the induction period and the Se(IV) concentration in the range between 0.9 and 9.6 ng/mL Se. Masking with EDTA and solvent extraction with diethyldithiophosphoric acid can be used for the separation of interfering elements forming complexes with the reagent.     

A novel and efficient oxidative biaryl coupling reaction of phenol ether derivatives using a combination of hypervalent iodine(III) reagent and heteropoly acid

A novel and efficient oxidative biaryl coupling reaction of phenol ether derivatives using a combination of hypervalent iodine(III) reagent, phenyliodine(III) bis(trifluoroacetate) (PIFA), and heteropoly acid has been developed.     

Separation of Periodate, Iodate and Iodide on a C-18 Stationary Phase. Dependence of the Retention on the Temperature and Solvent Composition. Monitoring of an Oxidative Cleavage Reaction

The separation of periodate, iodate and iodide can be easily achieved by HPLC on a C-18 column with a mobile phase consisting of acetonitrile and aqueous phosphoric acid, without the need of any mobile phase additives that are often employed. All three iodine species are well separated. Separation factors as high as 16 are observed, and retention factors k between ～0.5 and 8. The retention time of all three ions increases with increasing acetonitrile concentration. The retention time of periodate and iodide decreases with increasing temperature, however, it increases slightly for iodate. An application of the HPLC method that was developed is the monitoring of an oxidative cleavage reaction, the cleavage of the enone-group of the steroid 4-androstene-3,17-dione. Periodate is used as oxidative reagent for this reaction. During the reaction periodate is reduced to iodate, and eventually both iodine species will be present in the reaction mixture, besides the starting material and product. In the final product the remaining iodate ions will be reduced to iodide which can be quantified accurately using the developed HPLC method.     

Experimental study of a closed system in the sodium chlorite–iodine–ethyl acetoacetate oscillation reaction by UV–Vis and online FTIR spectrophotometric method

The sodium chlorite–iodine–ethyl acetoacetate (EAA) chemical oscillatory reaction system was studied by UV–Vis and online FTIR spectrophotometric method. The oscillation phenomenon does not occur as long as the reactants are mixed. There is a pre-oscillatory or induction period. The amplitude is small at the beginning stage and then increases with reaction time. Finally, the oscillation ceases suddenly. The amplitude and the number of oscillations are associated with the initial concentration of sodium chlorite, iodine, EAA and sulfuric acid. The equations for the triiodide ion reaction rate changing with reaction time and the initial concentrations on the oscillation stage were obtained. The intermediates were detected by the online FTIR analysis. Based upon the experimental data in this work and in the literature, a plausible reaction mechanism was proposed for the oscillation reaction.     

碘-聚乙烯醇显色法标定硫代硫酸钠溶液

聚乙烯醇和碘能够发生显色反应，在碘量滴定法的一些测定中，可以用聚乙烯醇代替淀粉作指示剂指示终点。分别用碘、碘酸钾作基准试剂，聚乙烯醇、淀粉作指示剂，对硫代硫酸钠溶液进行标定，测定结果基本一致。     

The efficient synthesis of morphinandienone alkaloids by using a combination of hypervalent iodine(III) reagent and heteropoly acid

The non-phenolic coupling reaction of benzyltetrahydroisoquinolines (laudanosine derivatives) by using a hypervalent iodine(III) reagent is described. In general, chemical oxidation of laudanosine gives glaucine. In contrast to general chemical oxidizing reagent systems, the novel use of reagent combination of phenyliodine bis(trifluoroacetate) (PIFA), and heteropoly acid (HPA) afforded morphinandienone alkaloids in excellent yields. In order to achieve the coupling reaction with simple reaction procedure, the use of HPA supported on silica gel instead of HPA was demonstrated and sufficient yield was exerted again. The present reagent system, PIFA/HPA, was also applied to the oxidation of other non-phenolic benzyltetrahydroisoquinolines and the high yield conversion to morphinandienones was accomplished.     

The hydrogen peroxide–iodic acid–manganese (ii)–acetone oscillating system: Further observations

The redox potential and iodine concentration behavior of the title reaction and component reactions have been examined. The effect of hydrogen peroxide, potassium iodate, manganese (II) sulfate, sulfuric acid, and acetone concentration on the time period and redox potential behavior is reported. Iodine production and consumption rates for the component reactions are given, and some mechanistic suggestions, involving iodine dioxide as the one electron oxidant, are made.     

原位生成的高价碘试剂在有机合成中的应用进展

原位生成的高价碘试剂具有原子经济性、性能温和和绿色环保等优点,在诸多合成和不对称催化等反应中表现活跃.详细介绍了原位生成高价碘的概念以及反应机理,根据不同的反应类型分别对原位生成的三价碘、五价碘以及手性高价碘试剂在有机合成反应中的应用进行了归纳总结,分析了原位生成的高价碘试剂目前面临的问题,并对今后的发展趋势作了展望.     

Reaction rates between water and the Karl Fischer reagent

Reaction rates between water and the Karl Fischer reagent have been determined by potentiometric measurement for various compositions of the Karl Fischer reagent. The study has been made with an iodine complex concentration of 0.3-1.2 mM and sulphur dioxide complex at 0.01-0.5M. The concentration of excess of pyridine had no measurable effect on the rate of the main reaction. The reaction was found to be first-order with respect to iodine complex, to sulphur dioxide complex, and to water. The rate constant was (1.2+/-0.2) x 10(3) 1(2). mole(-2). sec(-1). In an ordinary titration it is therefore essential to keep the sulphur dioxide concentration high for the reaction to go to completion within a reasonable time. The extent of side-reactions was found to be independent of the iodine concentration at low concentrations. The side-reactions increased somewhat with increasing sulphur dioxide pyridine concentrations and decreased to about 60% when the temperature was lowered from 24 degrees to 7 degrees.     

Experimental Study of a Closed System in the Chlorine Dioxide–Iodine–Ethyl Acetoacetate–Sulfuric Acid Oscillation Reaction by UV-vis and Online FTIR Spectrophotometric Methods

The appearance of oscillations for the closed system ClO₂–I₂–ethyl acetoacetate depends critically on the pH in the absence of sulfuric acid, and was investigated by determining changes in the absorbance of I₃ ^-\mathrm{I}_{3}^{ -} with reaction time at the wavelength 280 nm. The pH should be 2.2–3.8 for this reaction. The initial concentrations of ethyl acetoacetate, chlorine dioxide, iodine and sulfuric acid have great influences on the oscillations observed at wavelengths of 280 nm or 350 nm. The oscillations at 280 nm occur as long as the reactants are mixed. However, at 350 nm the oscillation is preceded by a pre-oscillatory or induction period. The oscillation curve is more regular and smooth at 350 nm than that at 280 nm. The amplitude and the number of oscillations are associated with the initial concentration of each reactant. (1) The higher the initial concentration of ethyl acetoacetate, the greater is the amplitude while the number of oscillations becomes smaller. The amplitude is small at the beginning stage but increases with reaction time. An opposite influence exists for chlorine dioxide. Finally, the oscillation suddenly ceases. (2) When the initial concentration of iodine is higher, the amplitude is small at the beginning stage but then increases with reaction time. When the initial concentration of iodine is lower, the amplitude is large at the beginning stage and then decreases with reaction time. An opposite influence exists for sulfuric acid. Equations for the triiodide ion reaction rate were obtained as functions of reaction time and initial concentrations at the oscillation stage. The intermediates were detected by online FTIR analysis. Based upon the experimental data in this work and in the literature, a plausible reaction mechanism was proposed for the oscillation reaction.     

Recyclable hypervalent iodine(III) reagent iodosodilactone as an efficient coupling reagent for direct esterification, amidation, and peptide coupling

A hypervalent iodine(III) reagent plays a novel role as an efficient coupling reagent to promote the direct condensation between carboxylic acids and alcohols or amines to provide esters, macrocyclic lactones, amides, as well as peptides without racemization. The regeneration of iodosodilactone (1) can also be readily achieved. The intermediate acyloxyphosphonium ion C from the activation of a carboxylic acid is thought to be involved in the present esterification reaction.     

Hofmann-type rearrangement of imides by in situ generation of imide-hypervalent iodines(III) from iodoarenes

The Hofmann-type rearrangement of aromatic and aliphatic imides using a hypervalent iodine(III) reagent generated in situ from PhI, m-CPBA, and TsOH·H(2)O proceeded in the presence of a base in alcohol to provide anthranilic acid derivatives and amino acid derivatives in high yields, respectively. This reaction proceeds through a tandem reaction via alcoholysis followed by a Hofmann rearrangement promoted by the formation of an imide-λ(3)-iodane intermediate.