Polarographic determination of phenylalanine,tyrosine, methionine,glutamic acid and histidine with a dropping copper amalgam electrode

The anions of the phenylalanine, tyrosine, methionine and glutamic acid give an anodic wave when a dropping copper amalgam electrode is oxidized in their presence, approximately at the same half-wave potential of that of the glycine anion (?0.28 V vs. SCE). The height of these waves depends on pH and amino acid concentration and can be utilized for the polarographic determination of these substances using the same procedure as that described previously for the determination of glycine. The polarographic behaviour of histidine is somewhat different because the zwitterion of this amino acid reacts with the Cu²⁺ and the anion forms a more stable complex. The polarographic determination of histidine can be also carried out with the same procedure.     

Intermittent Chaos in the Bray–Liebhafsky Oscillator. Dependence of Dynamic States on the Iodate Concentration

Chaotic dynamic states with intermittent oscillations were generated in a Bray–Liebhafsky (BL) oscillatory reaction in an isothermal open reactor i.e., in the continuously-fed well-stirred tank reactor (CSTR) when the inflow concentration of potassium iodate was the control parameter. They are found between periodic oscillations obtained when [KIO₃]₀ < 3.00 × 10^–2 M and stable steady states when [KIO₃]₀ > 4.10 × 10^–2 M. It was shown that the most chaotic states obtained experimentally somewhere in the middle of this region are in high correlation with results obtained by means of largest Lyapunov exponents and phenomenological analysis based on the quantitative characteristics of intermittent oscillations.     

Reduction mechanism of cobalt(II)-ammonia complexes on a dropping mercury electrode

The mechanism of the polarographic reduction of cobalt(II) complexes with ammonia at a dropping mercury electrode over a wide ligand concentration range was investigated. It was shown that the Co(II) aquo ion and the Co(NH₃)²⁺ and Co(NH₃²⁺₂ complexes participate in the electrode process. Transfer coefficients, α, for these species and the electrode reaction rates were evaluated. Stability constants of Co(II) complexes with ammonia in 0.5 M ammonium perchlorate were determined on the basis of the polarographic wave equation of totally irreversible reduction of complex specie.     

Oberflächenspannungstheorie der polarographischen Maxima erster Art

The purpose of this work is the presentation of a new theory about polarographic maxima. The applicability of the theory is proved on the system Cu²⁺Cu⁰.

     

A new experimental method to distinguish two different mechanisms for a category of oscillators involving mass transfer

We present new experimental evidence that further confirms that a combination of electrochemical reactions and diffusion–convection (ERDC) mass transfer accounts for the potential oscillations that appear under conditions of transport limited current. A typical example is given for the reduction of Fe(CN)₆³⁻ in alkaline solution accompanying periodic hydrogen evolution. No potential oscillations occur by simply replacing the hydrogen evolution with IO₃⁻ reduction as the second current carrier. That replacement removes only the convection mass transfer induced by the hydrogen evolution, and retains the negative differential resistance (NDR) from the Frumkin repulsive effect. The key role of hydrogen evolution is thus to restore the Fe(CN)₆³⁻ surface concentration after its depleting to zero by diffusion-limited reduction, rather than purely a second current carrier. Therefore, the other mechanism, which emphasizes the NDR from the Frumkin interaction due to electrostatic repulsion, is excluded because it does not have a direct connection with the oscillations. Moreover, a crossing cycle in cyclic voltammograms is a more convincible criterion for this category of electrochemical oscillators than the negative impedance.     

Polarographic Determination of Aztreonam

Abstract

The polarographic behaviour of Aztreonam is studied. In acid media, at pH values lower than 6, in differential pulse polarography a peak is observed at a potential close to ? 0.6 volts. The optimum conditions for the polarographic signal are established and the different parameters affecting the electrochemical process are studied. The relationship between peak intensity and the concentration of Aztreonam is linear for concentrations lower than 1.0 ? 10^?5 M, the detection limit being 1.4 × 10^?8 M It was observed that the presence of 1-arginine does not affect the polarographic signal of Aztreonam to any significant extent.     

Influence of metal ions on oscillatory behavior of zinc anode in nitric acid-potassium dichromate media

A zinc anode in acidic media is a new oscillatory electrochemical system which manifests interesting behaviors, from steady states to simple oscillations and chaos. This paper presents an experimental study of the influence of metal ions on the shape, amplitude and duration of the cell potential oscillations, and gives a qualitative explanation of the system’s behavior. A small quantity of Cu²⁺, Zn²⁺ or Fe³⁺ ions added to the system change dramatically the potential oscillations from chaotic behavior to simple oscillations. The method may be used for chaos attenuation.     

Polarographic waves of tri-n-butyl phosphate and polarographic determination of uranium in the presence of tri-n-butyl phosphate

The results of a study on the polarographic behaviour of TBP and its influence on the determination of uranyl ions is presented. The half-wave potential of the adsorption wave of TBP depends on the concentration of TBP, type of supporting elec trolyte and its concentration. In the presence of TBP the polarographic wave of U(VI) ion is changed. Below 7·10^?5 M TBP the polarographic wave of U(VI) is not affected, between 7·10^?5 and 2·10^?4 M TBP the shape, height and half-wave potential of U(VI) waves are changed and above 2·10^?4 M, up to saturated solution of TBP, the waves of U(VI) do, not change further. The bes supporting electrolytes for the determination of U(VI) are KNO₃ or NaClO₄ in concentrations of 0.1 to 0.5 M, pH 1–2 and TBP concentrations from 3·10^?4 to 1.2·10^?3 M.     

Study of Complex Formation between 5,7‐Diiodo‐8‐hydroxyquinoline and Zn2+, Cd2+, Pb2+ and Tl+ Cations in Binary Non‐Aqueous Solvents Using Square Wave Polarography Technique (SWP)

The complexation reaction between Zn²⁺, Pb²⁺, Cd²⁺ and Tl⁺ cations by 5,7‐diiodo‐8‐hydroxyquinoline (IQN) was studied in the Dimethylformamide /Acetonitril (DMF‐AN) binary system using square wave polarography technique. The stoichiometry and stability of the complexes were determined by monitoring the shifts in half‐wave or peak potential of the polarographic waves of metal ions against the ligand concentration. The stoichiometry of the complexes was found to be 1:1. The results obtained show that there is an inverse relationship between the formation constant of the complexes and the donor number of solvent base on the Guttmann donocity scale. In all cases the formation constants increased with increasing amounts of AN in these binary systems. The selectivity order for IQN complexes with the cations is Zn²⁺ > Pb²⁺ > Cd²⁺ > Tl⁺.     

Catalytic Kinetic Determination of Trace Amounts of Iron(III) With Polarographic Detection

Abstract

This method is based on the catalytic effect of Fe³⁺ on the oxidation reaction between Acid Chrome Blue K and potassium bromate in sulfuric acid medium at 100deg;C, and in 0.08 mol/L NH₄OH - 0.01 mol/L (NH₄)₂ SO₄ supporting electrolyte, Acid Chrome Blue K exhibits a sensitive polarographic wave at -0.55V vs. SCE, and change of concentration is traced by a polarographic detection technique. The linear range of Fe³⁺ is 10–100ng/mL. This new catalytic method has been applied to the determination of iron in natural water and food with satisfactory results.     

487—Polarographic study of zinc binding to glutamate dehydrogenase

The interaction of glutamate dehydrogenase with zinc ions was analysed by d.d.p. and n.p.p. The n.p. polarograms of the equimolar enzyme-Zn²⁺ mixtures consists of a wave with a maximum if scanned using low pulse widths. Two peaks (peak I at about ? 1.0 V and peak II at about ? 1.5 V) were observed in d.p.p. polarograms of the enzyme-Zn²⁺ mixtures. The behaviour of summit potentials and peak heights under various polarographic conditions was investigated.Peak I was attributed to the reduction of free zinc ions with a minor contribution of the enzyme-Zn²⁺ complex split at the electrode surface. The complex contribution can be suppressed if short delays are used. The polarographic titration of the enzyme with Zn²⁺ can be utilized for the determination of the dissociation constant and/or binding sites concentration. Peak II observed at short delays even in the presence of the enzyme alone, has the basic features of catalytic peaks.     

Numerical evidence of complex nonlinear phenomena of the Belousov-Zhabotinsky oscillatory reaction under batch conditions

By numerical calculations based on our previously proposed model with Br₂O intermediate species we were able to simulate complex evolution of the Belousov-Zhabotinsky (BZ) reaction under batch conditions. In the defined region of initial malonic acid concentration [MA]₀ (1.00 × 10^?3 mol dm³ ≤ [MA]₀ ≤ 1.50 mol dm^?3) different sequences of regular and complex periodic and aperiodic oscillations were obtained. It is noticed that the bromine evaporation significantly affects the dynamics of the reaction.     

Size and shape dependence of the electrostatic potential in cluster models of the MgO(100) surface

We investigated the dependence of the electrostatic potential on the size and the shape of various cluster models of the MgO(100) surface. Both Mg²⁺ and O²⁻ adsorption sites have been considered. The clusters were embedded in a large array of point charges to provide a representation of the Madelung potential. We found that the electrostatic potential in the adsorption region shows a marked dependence on the size of the cluster, in particular, for non-stoichiometric clusters where the number of cations and anions differs considerably. These oscillations are due to (a) the different contribution to the electrostatic potential given by a point charge or by an extended ion, and (b) by the polarization of the ions at the cluster border. The effect of the oscillations in the electrostatic potential on the chemisorption properties was investigated for the case of CO₂ interacting with surface and defect O²⁻ sites of the MgO surface. © 1996 John Wiley & Sons, Inc.     

Enoxacin: Polarographic Behaviour and Its Determination in Pharmaceutical Forms

Abstract

A differential pulse polarographic method for the identification and quantitative determination of enoxacin is described. The method is based on the electrochemical reduction of the drug at the dropping mercury electrode. It gives a well-developed polarographic response with a half-wave potential of -990 mV vs. SCE in 0.1 M HCl. The electroactive specie exhibits a diffusion-controlled polarographic wave and its limiting current shows a linear dependence with the enoxacin concentration in the range between 5.10^?4 mM and 1 mM. This characteristic is applied for determination of enoxacin in commercial tablets. The recovery study shows a good accuracy and precision for the developed assay (average of 101.1% and standard deviation of 1.99). Furthermore, a comparative UV spectrophotometric assay also is developed.     

Differential-pulse polarographic determination of chromium and nickel in zircaloys using microsamples

Three methods were developed for the analysis of the alloying elements chromium and nickel in Zircaloy-2 and Zircaloy-4, alloys of zirconium used extensively in the nuclear industry as nuclear fuel sheathing. Zircaloy was dissolved in hydrofluoric acid followed by oxidation of Cr(III) to Cr(VI) by perchloric acid. The polarographic peak of CrO ₄ ^2– in alkaline medium was used to determine Cr. Nickel was determined, after HF dissolution, using the polarographic peak of the nickel-ammonia complex, Ni (NH₃) ₆ ²⁺ . In an alternative method for Ni, the sample was dissolved in HF and the polarographic peak of the nickel-fluoride complex, NiF ₄ ^2– , was used. Careful control of fluoride ion concentration and the pH eliminated the harmful effect of fluoride on the capillary behaviour of the dropping mercury electrode. The detection limits for chromium, nickel-ammonia and nickel-fluoride in Zircaloys were 0.0016, 0.0033, and 0.0041%, respectively.     

A Polarographic Study on Dipyridamole and its Determination in Commercial Tablets

Abstract

The direct current polarographic behaviour of dipyridamole, a coronary vasodilator, in the supporting electrolyte consisting of 0.2 M KCl, 20 % (v/v) ethanol and buffer solutions is described in this study. Morphologically well-defined DC polarographic curves have appeared within the pH range of 7–8 and the optimum polarographic conditions found were, a potential rate of 4 m V.s^?1, drop time of 1 s and a pressure of 1000 dyne.cm^?2. The factor effecting the polarographic current was diffusion-controlled and the reduction reaction was highly reversible. The effect of concentration on the limiting current was examined using DC, SCAP, SIAP and DP polarographic modes at pH 7.8 and optimum conditions. Linear calibration equations with good correlations were obtained for all techniques. DP polarography was used among the modes for the determination of dipyridamole in the tablets. The results obtained were compared with the results of the UV-spectrophotometric method. Using the Mann-Whitney U-test, it was concluded that there is an insignificant variance between the two methods. The relative standard deviations are 75±1% and 75.3±0.7% for DP polarographic and UV-spectrophotometric methods, respectively. The determination method proposed in this study seems to be accurate, rapid and practical. Therefore, it may be suitable for the content uniformity test (USP XXI).     

A Polarographic Study of Tl+, Pb2+ and Cd2+ Complexes with Aza-18-crown-6 and Dibenzopyridino-18-crown-6 in some Binary Mixed Non-aqueous Solvents

The complexation of Tl⁺, Pb²⁺and Cd²⁺ cations by macrocyclic ligands, aza-18-crown-6 (L1) and dibenzopyridino-18-crown-6 (L2) was studied in some binary mixtures of methanol (MeOH), n-propanol (n-PrOH), nitromethane (NM) and acetonitrile (AN) with dimethylformamide (DMF) at 22 °C using DC (direct current) and differential pulse polarographic techniques (DPP). The stoichiometry and stability constants of the complexes were determined by monitoring the shifts in half-waves or peak potentials of the polarographic waves of metal ions against the ligand concentration. In all of the solvent systems, the stability of the resulting 1:1 complexes was found to be L1 > L2. The selectivity order of the L2 ligand for the cations was found to be Pb²⁺ > Tl⁺ > Cd²⁺ and the selectivity of the L1 ligand for Pb²⁺ ion was greater than that of Tl⁺ ion. The results show that the stability of the complexes depends on the nature and composition of the mixed solvents. There is an inverse relationship between the stability constants of the complexes and the amount of dimethylformamide in the mixed solvent systems.     

Exploration of Pb2+ Selective Behavior of Calix[6]arene Ester Derivative

The selective behavior of calix[n]arene ester derivatives in two-phase extraction systems using polarographic technique has been investigated. Calix[4]arene tetraester derivative shows remarkable Na⁺ over Pb²⁺ selectivity; whereas calix[6]arene hexaester derivative shows Pb²⁺ over Na⁺ selectivity. The interference of some selected cations (Na⁺, K⁺, Cu²⁺ and Mg²⁺) were also examined and no significant effect on the selectivity behavior as well as extraction ability of these ionophores was found except Na⁺. The study reveals for the first time that the calix[6]arene hexaester derivative is highly Pb²⁺ selective ionophore and can be employed in the field of sensor as well as separation science and technology. The work also highlights the usefulness of polarographic technique in trace metal determination.     

界面缓蚀剂的吸附稳定性

研究表明：在一定条件下,阳极脱附电位可作为评价缓蚀剂吸附稳定性的一个经验参数：缓蚀剂吸脱附诱导的电化学振荡是缓蚀体系的一种特殊失稳状态,即缓蚀剂吸附过程与电极反应中间吸附态产物耦合的结果;卤素离子的协同作用不仅可以提高某些有机缓蚀剂的吸附复盖度,而且可以增强其吸附稳定性;微分极化曲线是研究吸附稳定性的有效方法。     

Oscillations chimiques du système BrO/Ce4+/acétylacétone. Communication préliminaire

Temporal chemical oscillations occurring in the BrO₃^?/Ce⁴⁺/acetylacetone system have been investigated by three different methods: potentiometry, calorimetry and NMR. spectrometry. In spite of the analogy between acetylacetone and malonic acid, this periodic reaction seems to be rather different from the famous Belousov-Zhabotinsky reaction.