Potential response in the uncatalyzed bromate oscillatory system

The potential response of the platinum indicator electrode in the uncatalyzed bromate oscillator (UBO) with three different substrates, namely gallic acid (GA), pyrogallol (PG) and veratraldehyde (VA) has been analyzed. The large amplitude oscillations obtained with a Pt electrode are due to the sequential response of the indicator electrode to the varying concentration ratios of the redox couples present in the reaction mixture.     

The coulometric titration of bromate with cuprous copper

A coulometric procedure has been developed by which 18 to 240 μg quantities of bromate may be determined to within 0.3 μg. The bromate is allowed to react with bromide in an acid solution and electrolytically generated cuprous copper is used for the titration. A dual platinum electrode indicator system is used in an amperometric end-point procedure     

A catalytic method for the determination of trace osmium in continuous flow and flow injection systems

A procedure has been developed for the determining osmium using a catalytic indicator reaction of arsenic(III) oxidation with potassium bromate and neutral red in continuous flow and flow injection systems. The possibilities of the flow systems have been compared on an example of the proposed reaction, and the regularities of this reaction conducted in different flow systems have been revealed. Recommendations on the choice of the optimal variant of the flow system are given. The accuracy of the procedure has been confirmed by the results of determining osmium in a State Reference Sample.     

Spectro photometric determination of bromate with o-arsanilic acid

o-Arsanilic acid reacts with bromate ions in dilute acid solution and forms a reddish-brown color which is suitable for the spectrophotometric determination of bromate. The reaction has a sensitivity of 0.05 μg BrO₃^- per cm2 for log $\text{I}{}_{\mathrm{o}}\text{l}$ = 0.001 and obeys Beer's law up to 50 p.p.m.The standard deviation for the color development (387 p.p.m. brornate) is 0.95%, and 0.52% in the determination of bromate in salt solutions.Optimum analytical conditions for the reaction have been established and a procedure for the spectrophotometric determination of bromate is given.     

The application of the ph-stat method to metal ion-catalyzed reactions

The pH-stat method, which is well known in organic chemistry and biochemistry, is used for the kinetic determination of metal ion catalysts. Indicator reactions that involve protons can be followed by controlled addition of standard base or acid. This is illustrated by the following examples: determination of copper(II) (0.03–0.3 μg ml^-1) with the indicator reaction ascorbic acid—peroxydisulphate; determination of molybdenum(VI) (0.2–2.5 μg ml^-1) with the indicator reaction thiosulphate—hydrogen peroxide; determination of zirconium(IV) (0.2–2 μg ml^-1) with the indicator reaction iodide—hydrogen peroxide; and determination of vanadium(V) (0.2–2 μg ml^-1) with the indicator reaction iodide—bromate. For one example, the copper—ascorbic acid—peroxydisulphate reaction, it is shown that the pH-stat method has distinct advantages over closed systems, giving considerably better sensitivity for the determination of copper (0.5–5 ng ml^-1 ).     

A chemical oscillator based on the photoreduction of 2-methyl-1,4-benzoquinone

This study investigated bromate-2-methyl-1,4-benzoquinone photoreaction in a batch reactor, in which the photoreduction of 2-methyl-1,4-benzoquinone plays a vital role in initiating and sustaining the reaction process. Transient oscillatory phenomena are observed over broad reaction conditions, but a phase diagram in the bromate and sulfuric acid concentration plane shows that the nonlinear behavior is more sensitive to the ratio of bromate and acid than their absolute concentrations. Light intensity and the photosensitive substance 2-methyl-1,4-benzoquinone exhibited opposite effects on the induction time of these oscillations, implying that illumination does more than just reduce 2-methyl-benzoquinone. The oscillatory behavior has been qualitatively reproduced with a generic model developed for bromate-aromatic compounds systems.     

Transient Chemical Oscillations in the 4‐(N,N‐Dimethylamino) Benzoic Acid–Bromate Reaction

The bromination and oxidation of 4‐(N,N‐dimethylamino) benzoic acid (DMABA) by acidic bromate was investigated in a batch reactor through following their redox potential and UV/vis absorption spectra, in which transient oscillations with a long induction time were observed. Different from most of the bromate‐aromatic compound oscillators reported earlier, the addition of metal catalysts such as manganese, cerium, and ferroin does not significantly affect the nonlinear phenomena, but the induction time could be greatly shortened by adding bromide ions as a starting reagent. The reaction between bromine and DMABA was identified through ¹H NMR spectroscopy to form 3‐bromo‐4‐(N,N‐dimethylamino) benzoic acid. The compound 3‐bromo‐DMABA was also found to occur relatively early during the bromate‐DMABA reaction and was determined to be a major component prior to the onset of oscillations. Periodic evolution of 3‐bromo‐4‐(N,N‐dimethylamino) benzoic acid has been detected with a UV/vis spectrophotometer.     

Catalytic kinetic determination of ultratrace amounts of nitrite with detection by linear scan voltammetry at a DME

Nitrite has a very strong catalytic effect on the bromate oxidation of Methyl Orange in dilute sulphuric acid medium. The oxidation product of methyl orange exhibits a well derivative voltammetric wave at -0.41 V vs. SCE in sodium hydroxide medium. The linear scan voltammetric behaviour for the product at a DME has been studied, and it was selected as indicator component for the indicator reaction. Based on these studies, a novel and highly sensitive and selective catalytic reaction-voltammetric method for nitrite is proposed. A detection limit of 2 x 10(-9)M and calibration graph from 4 x 10(-7) to 4 x 10(-7)M nitrite are obtained. Nitrite in water samples was determined by this method, with satisfactory results.     

Flow Injection Catalytic Determination of Vanadium using the Indicator Reaction between Victoria Blue B and Bromate and A Citric Acid Activator

ABSTRACT

A flow injection catalytic method is proposed for determination of trace vanadium based on its catalytic action on a new indicator reaction between Victoria blue B (VBB) and potassium bromate in the presence of citric acid as an activator and in dilute sulfuric acid medium. The reaction is monitored spectrophotometrically by measuring the decrease in absorbance of VBB injected at the maximum absorption wavelength of 618 nm. The detection limit is 0.5 ng ml^?1 and is independent of the initial valence state of vanadium. The relative standard deviation is 1.5% obtained from 11 standard solutions each containing 40 ng ml^?1 of vanadium. The sampling rate is about 15 samples per hour. This method is very simple and has been applied to the determination of trace vanadium in some natural waters with recoveries of 93-103%.     

Kinetic and mechanism of oxidation of thiocarbohydrazide and its metal complex by acid bromate in aqueous and partial aqueous media

The kinetics of oxidation of thiocarbohydrazide in the free and zinc(Ⅱ)-bound states byacid bromate have been studied in aqueous and water-acetic acid(1:1,V/V)media under varyingconditions,both in the absence and presence of added bromide ion.The rates of oxidations show firstorder kinetics in[bromate]in all the cases,but exhibit different kinetic behaviour in[substrate]and[H~+].Oxidation of TCH in aqueous medium shows zero order in[TCH]and nearly second order in[H~+],while oxidation in aqueous acetic acid shows two ranges in[H~+].The rate shows first and fractionalorder kinetics in[TCH]in the first and second acid ranges.Kinetics observed in the presence of Br~-are similar to those observed for oxidation of TCH in second acid range.In addition,the reactionshows fractional order in[Br~-].Oxidation of TCH in Zn(Ⅱ)-bound state exhibits first order kinetics in[substrate]and second order in[H~+].Increase in ionic strength of the medium decreases the rate in allthe cases.Increase in acetic acid composition of the solvent increases the rate.Mechanisms consistentwith the observed results have been considered and the rate laws deduced.The rate limiting steps havebeen identified and the coefficients of these steps have been calculated at different temperatures.Therelated activation parameters have also been computed.The validity of the deduced rate laws has alsobeen tested by recalculating the rate constants from them as[TCH]and[H~+]are varied.     

Bromometric determination of carbimazole

Direct bromometric titration of carbimazole using N-bromosuccinimide (NBS) in the presence of methyl red as indicator and three indirect titrations using NBS, potassium bromate and dibromohydantoin (DBH) are developed. The direct procedure can be adopted for quantities of carbimazole ranging from 2-12 mg with mean accuracies of 100.2 +/- 0.5. The indirect procedures can be used for quantities of the drug ranging from 1-6 mg using NBS and DBH and 2-16 mg using potassium bromate with mean accuracies of 100.11 +/- 0.3, 100.49 +/- 0.31 and 100.26 +/- 0.51 respectively. The proposed procedures have been successfully applied for the analysis of the drug in tablet form and their validity has been checked using the standard addition technique. The reaction products were separated by TLC methods and their structure was elucidated using IR and NMR spectroscopy. The stoichiometry and the possible pathways of the reaction were postulated and presented.     

Volumetric studies in oxidation-reduction reactions: Reduction with ferrous ethylenediamine sulphate ceric sulphate method

Ferrous ethylenediamine sulphate has been used as a reducing agent in acid medium for the indirect volumetric estimations of potassium chlorate, potassium bromate, potassium metaperiodate, potassium dichromate, potassium ferricyanide, potassium permanganate, potassium persulphate, hydrogen peroxide and ceric sulphate. The excess of ferrous ethylenediamine sulphate added to each of the substances in acid medium was titrated with standard ceric sulphate solution using ferroin as an indicator.     

Reversible indicators for use in potassium bromate titrations

A review has been given of reversible indicators for use in bromate titrations. An examination has been made of four reversible indicators, α-naphthoflavone, p-ethoxy-chrysoidine. fuchsin and apomorphine.' All four indicators are satisfactory, but α-naphtho-flavone gives the sharpest end-points. Fuchsin and p-cthoxychrysoidine are gradually destroyed when the end-point is passed and re-passed several times. Apomorphine is only suitable for the titration of trivalent antimony and the end-point is the least sharp of all four indicators.Only α-naphthoflavone is suitable for the titration of 8-hydroxyquinoline solutions. Although it is possible to titrate directly and even back-titrate with standard 8-hydroxyquinoline, the method is not suitable because of the slow reaction between bromine and 8-hydroxyquinoline. The titration can be carried out satisfactorily, however, by adding excess bromate, then excess arsenite and re-titrating with bromate. The other two indicators are not suitable for this purpose; in the direct titration they tend to be destroyed by prolonged contact wth the excess bromine which is always present and, in any case, their colours are obscured by that of the 8-hydroxyquinoline so that the back-titration method is unsatisfactory.Aluminium can be determined satisfactorily after precipitations as the 8-hydroxyquinolate by titration with bromate and arsenite using α-naphthoflavone as indicator.     

Catalytic determination of ultra trace amounts of vanadium with detection by linear sweep voltammetry

Vanadium has a very strong catalytic effect on the bromate oxidation of gallocyanine at pH of 4.0. The oxidation product of gallocyanine exhibit a voltammetric wave at + 0.10 V vs. Ag/AgCl reference electrode in 0.10 mol/l KNO₃ medium. The linear scan voltammetric behaviour of the reaction products at HMDE has been studied and selected as the indicator component for the reaction. A detection limit of 0.05 ng/ml and calibration graph from 0.30–200.00 ng/ml vanadium were obtained. Vanadium in water and gasoline samples was determined by this method, with satisfactory results.     

Photokinetic voltammetric method for the determination of thiocyanate

Thiocyanate traces have a strong inhibitory effect on the oxidation of Neutral Red by potassium bromate under UV irradiation in diluted phosphoric acid. Neutral Red exhibits a sensitive second derivative oscillopolarographic wave at –0.6 V(vs. SCE) in diluted phosphoric acid and sodium acetate solution. The oscillopolarographic behavior of Neutral Red was selected as indicator component for its photo-activated oxidation. The photochemical reaction rate equation was determined. A detection limit of 0.3 ng mL^–1 (3σ/k) and a linear calibration curve from 2.0–48.0 ng mL^–1 thiocyanate were obtained. The method was applied to the determination of thiocyanate in urine, saliva and serum with satisfactory results.     

S-oxygenation of thiocarbamides. 3. Nonlinear kinetics in the oxidation of trimethylthiourea by acidic bromate

The oxidation of trimethylthiourea (TMTU) by acidic bromate has been studied. The reaction mimics the dynamics observed in the oxidation of unsubstituted thiourea by bromate with an induction period before formation of bromine. The stoichiometry of the reaction was determined to be 4:3, thus 4BrO(3)- + 3R(1)R(2)C=S+ 3H(2)O --> 4Br- + 3R(1)R(2)C=O + 3SO(4)(2-) + 6H+. This substituted thiourea is oxidized at a much faster rate than the unsubstituted thiourea. The oxidation mechanism of TMTU involves initial oxidations through sulfenic and sulfinic acids. At the sulfinic acid stage, the major oxidation pathway is through the cleavage of the C-S bond to form a reducing sulfur leaving group, which is easily oxidized to sulfate. The minor pathway through the sulfonic acid produces a very stable intermediate that is oxidized only very slowly to urea and sulfate. The direct reaction of aqueous bromine with TMTU was faster than reactions that form bromine, with a bimolecular rate constant of (1.50 +/- 0.04) x 10(2) M(-1) s(-1). This rapid reaction ensured that no oligooscillatory bromine formation was observed. The oxidation of TMTU was modeled by a simple reaction scheme containing 20 reactions.     

The 1,4-cyclohexanedione-bromate-acid oscillatory system I. Its organic chemistry

The organic chemistry of the 1,4-cyclohexanedione (CHD)-bromate-sulfuric acid oscillatory system has been revealed by following the reaction of 1,4-CHD with bromate using a GC/MS technique. We could identify 1,4-dihydroxybenzene as an intermediate, 1,4-benzoquinone as the main oxidation, and mono- and dibromocyclohexanedione as the main bromination products. Acid bromate does not cleave the alicyclic ring.     

Oscillatory reduction of bromate by aspirin in acidic aqueous solution

Summary The experimental behavior of the uncatalyzed Belousov - Zhabotinsky reaction between aspirin and bromate in acidic media in the batch reactor has been studied for the first time. Aspirin is an interesting substrate because it is one of the most used medicines. The medical aspirin behaves also in an oscillatory manner with bromate. The oscillating process was investigated under aerobic and anaerobic conditions. The complex dynamic behavior has been observed in the mixed aspirin - vitamin C - _BrO3 - H₂SO₄ system.     

Potassium Bromate-Thiourea Redox Initiated Grafting of Methyl Methacrylate onto Polyethylene Terephthalate

Some kinetic features of the grafting of methyl methacrylate onto polyethylene terephthalate initiated by the potassium bromate-thiourea redox system have been investigated in aqueous solution. The effects of potassium bromate, thiourea, monomer, acid, and temperature upon percentage grafting have been determined. The activation energy of the reaction has been computed from an Arrhenius plot. Grafting experiments have been carried out in the presence of such conventional chain-transfer agents as CC1₄ and CHC1₃. The effect of CuSO₄ upon grafting is also studied. The reaction mechanism involved during grafting is pictured.