CYCLIC VOLTAMMETRIC STUDY OF QUININE DERIVATIVES TRANSFER ACROSS THE WATER NITROBENZENE INTERFACE

Quinine derivatives, quinine hydrochloride and 8-hydroxyquinoline, transfer across the water/nitrobenzene interface was studied by cyclic voltammetry. The effect of solution acidity on the transfer behaviour was observed. Transfer mechanism was discussed

ELECTROCATALYTIC OXIDATION AND AMPEROMETRIC DETERMINATION OF SULFHYDRYL COMPOUNDS AT A COPPER HEXACYANOFERRATE FILM GLASSY-CARBON ELECTRODE IN LIQUID-CHROMATOGRAPHY

Electrocatalytic oxidation of sulfhydryl compounds was effective on a copper hexacyanoferrate (CuHCF) film glassy carbon electrode, at a significantly reduced overpotential (0.55 to 0.65 V) and for a broader pH range (2.0 to 7.0). The electrocatalysis was

RAPID-DETERMINATION OF KINETIC-PARAMETERS FOR THE ELECTROCATALYTIC REDUCTION OF DIOXYGEN BY VITAMIN-B12 ADSORBED ON GLASSY-CARBON ELECTRODE

In this paper, the electrochemical behavior of vitamin B-12, ie cyanocobalamin (abbr. VB12) in a weak acidic aqueous solution and adsorbed on glassy carbon (GC) surface (abbr. VB12(ad)/GC) in different pH buffer solutions have been described by using cyclic voltammetry (cv). It is found that VB12 and VB12(ad)/GC exhibit catalytic activity for the electroreduction of O2 according to two reduction peaks at -0.50 and -1.00 V vs. sce; but their electrocatalytic activity is very unstable. Based on the method of hydrodynamic amperometry [B. Miller and S. Bruckenstein, J. electrochem. Soc. 117, 1033 (1970)], some kinetic parameters for the electrocatalytic reduction of O2 by VB12(ad)/GC have been determined rapidly by using a linear rotation-scan method [Rongzhong Jiang and Shaojun Dong, Electrochim. Acta 35, 1451 (1990)]. These kinetic parameters indicate that the reduction of O2 on VB12(ad)/GC gives water predominantly in both potential ranges which correspond to those two reduction peaks. Possible reaction mechanisms have been suggested.

PREPARATION AND CHARACTERIZATION OF A MULTICYLINDER MICROELECTRODE COUPLED WITH A CONVENTIONAL GLASSY-CARBON ELECTRODE AND ITS APPLICATION TO THE DETECTION OF DOPAMINE

A multi-cylinder microelectrode coupled with a conventional glassy carbon disc electrode (MCM/GC) was prepared and characterized using cyclic voltammetry and chronoamperometry. It was demonstrated that in the same way as one observed a steady-state current at closely spaced microelectrodes when redox recycling takes place, the same effect can be obtained with the MCM/GC device. The experimental results obtained with K3Fe(CN)6 solutions were compared with a previously developed theory. Further, it was demonstrated that with a carbon fibre MCM/GC device, the voltammetric behaviour of dopamine is greatly improved by virtue of redox recycling, hence giving high sensitivity. The steady-state collection current was linearly related to dopamine concentration in the range 1 X 10(-4) to 5 x 10(-7) Mol l-1, and the detection limit was 2 x 10(-7) mol l-1. The influence of coexisting ascorbic acid was also investigated. This device was applied successfully in the determination of dopamine hydrochloride in pharmaceutical preparations.

DETERMINATION OF INITIATION VALUE OF MODE-I INTERLAMINAR FRACTURE-TOUGHNESS OF UNIDIRECTIONAL POLYMER COMPOSITES

The use of interlaminar fracture tests to measure the delamination resistance of unidirectional composite laminates is now widespread. However, because of the frequent occurrence of fiber bridging and multiple cracking during the tests, it leads to artificially high values of delamination resistance, which will not represent the behavior of the laminates. Initiation fracture from the crack starter, on the other hand, does not involve bridging, and should be more representative of the delamination resistance of the composite laminates. Since there is some uncertainty involved in determining the initiation value of delamination resistance in mode I tests in the literature, a power law of the form G(IC) = A.DELTA alpha(b) (where G(IC) is mode I interlaminar fracture toughness and DELTA alpha is delamination growth) is presented in this paper to determine initiation value of mode I interlaminar fracture toughness. It is found that initiation values of the mode I interlaminar fracture toughness, G(IC)(ini), can be defined as the G(IC) value at which 1 mm of delamination from the crack starter has occurred. Examples of initiation values determined by this method are given for both carbon fiber reinforced thermoplastic and thermosetting polymers.

ELECTROCATALYSIS AND DETERMINATION OF HYDRAZINE COMPOUNDS IN LIQUID-CHROMATOGRAPHY AT A MIXED-VALENT COBALT OXIDE CYANOCOBALTATE FILM ELECTRODE

A glassy carbon electrode coated with an electrodeposited film of mixed-valent cobalt oxide/cyanocobaltate (Co-O/CN-Co) enabled hydrazine compounds to be catalytically oxidized at the greatly reduced overpotential and in a wide operational pH range (pH 2.0-7.0). Electrocatalytic activity at the Co-O/CN-Co modified electrode was evaluated with respect to solution pH, film thickness, supporting electrolyte ions, potential scan rate, operating potential, concentration dependence and other variables. The Co-O/CN-Co film electrode was completely compatible with a conventional reversed-phase liquid chromatographic (RP-LC) system. Practical RP-LC amperometric detection (RP-LCEC) of hydrazines was performed. A dynamic linear response range over three orders of magnitude and a detection limit at the pmol level were readily obtained. The Co-O/CN-CO film electrode exhibited excellent electrocatalytic stability in the flowing streams.

FACTOR-ANALYSIS SPECTROPHOTOMETRY FOR THE SIMULTANEOUS DETERMINATION OF VALENCE STATES OF METALS

Two M(n+)-2-(5-bromo-2-pyridylazo)-5-diethylaminophenol systems for the simultaneous determination of the valence states of Cr and Fe using factor analysis were studied. (1) At pH 4.0, Cr(III) and Cr(VI) react with the reagent to form stable complexes and a slight difference in the wavelengths of maximum absorption (lambda(max.)) between the two complexes is observed when the sodium lauryl sulfate, which also acts as a solubilizing and sensitizing agent, is added, viz., 590 nm for Cr(III) and 593 nm for Cr(VI) complexes. (2) In the presence of ethanol, both Fe(II) and Fe(III) form 1:2 complexes with the reagent at pH 2.5-3.5 and the lambda(max.) of the Fe(II) and Fe(III) complexes is at 557 and 592 nm, respectively. In the target transformation factor analysis, the K coefficients calculated from the standard mixtures by classical least-squares analysis and a non-zero intercept added to each wavelength are used as the target vector instead of the pure component standards; this can decrease the analysis errors introduced by the interaction between the two species and by deviations from Beer's law.

APPLICATIONS OF RAPID SCAN SPECTROELECTROCHEMISTRY - DETERMINATION OF HETEROGENEOUS ELECTRON-TRANSFER RATE-CONSTANT OF BILIVERDIN OXIDATION

The rapid scan spectrometer was used to determine the heterogeneous electron transfer rate parameters for the oxidation of Biliverdin in DMF by single potential step thin layer spectroelectrochemical techniques and yielded an average formal heterogeneous electron transfer rate constant K(s, h)0' = 2.45 (+/-0.12) x 10(-4) cm s-1, electrochemical transfer coefficient alpha = 0.694+/-0.008. The oxidation process of Biliverdin was also studied and the formal potential E0 = 0.637 V (vs. Ag/AgCl) was obtained.

THE APPLICATION OF AN ULTRAMICROELECTRODE IN HOMOGENEOUS CATALYTIC REACTION .1. GENERAL CHARACTERISTIC OF A HOMOGENEOUS CATALYTIC REACTION AT AN ULTRAMICROELECTRODE WITH ARBITRARY GEOMETRY UNDER STEADY-STATE

A general characteristic of the electrochemical process coupling with a homogeneous catalytic reaction at an ultramicroelectrode under steady state is described. It was found that the electrochemical process coupling with homogeneous catalytic reaction has a similar steady state voltammetric wave at an ultramicroelectrode with arbitrary geometry. A method of determination for the kinetic constant of homogeneous catalytic reaction at an ultramicroelectrode with arbitrary geometry is proposed.

DETERMINATION OF THE RATE-CONSTANT OF A CATALYTIC REACTION USING A PARALLEL INCIDENT SPECTROELECTROCHEMICAL CELL

The possibility of determining the rate constant of a catalytic reaction using a parallel incident spectroelectrochemical cell was investigated in this work. Various spectroelectrochemical techniques were examined, including single-potential-step chronoabsorptometry, single-potential-step open-circuit relaxation chronoabsorptometry and double-potential-step chronoabsorptometry. The values determined for the kinetics of the ferrocyanide-ascorbic acid system are in agreement with the reported values. The parallel incident method is much more sensitive than the normal transmission method and can be applied to systems which have smaller molar absorptivities, larger rate constants or lower concentrations.

DETERMINATION OF THE MOLECULAR-ORIENTATION OF A PHTHALOCYANINE DERIVATIVE IN A LANGMUIR-BLODGETT-FILM BY POLARIZED UV VIS SPECTRA

Langmuir-Blodgett (LB) films of (p-carboxyphenoxy)-tri(2,4-di-tert-pentyl phenoxy)phthalocyanine copper(II) (asyCuPc) are prepared; the associated forms of the compound in chloroform solution and the particular orientation of asyCuPc molecular macrocycles in LB films is determined by polarized UV-VIS.

CYCLIC VOLTAMMETRIC AND SPECTROELECTROCHEMICAL STUDIES OF COPPER IN ALKALINE-SOLUTION

The behaviour of the electroplated copper film electrode on tin oxide/glass or glassy carbon surface was studied in potassium hydroxide medium by cyclic voltammetry and in situ transmission spectroelectrochemistry. The results indicate that the electroplated copper film electrode is similar to a copper electrode and cyclic voltammetry with this electrode affords more resolution. The anodic peaks were found to correspond successively to the adsorption of oxygen, the formation of a surface layer of Cu2O, the formation of a surface layer of Cu(OH)2 or CuO and formation of a thick multilayer film of CuO. This is the first time it has been proposed that a surface layer of Cu(OH)2 or CuO is formed from the oxidation of the surface layer of Cu2O. Similarly, a clear interpretation is presented that the cathodic peaks correspond successively to the reduction of CuO to Cu2O, the reductions of Cu2O to Cu and the soluble Cu(II) species to Cu. On the other hand, a shoulder peak related to the chemical transformation of Cu(OH)2 to CuO was first observed.

EASTMAN-AQ/NIII MODIFIED ELECTRODE CHARACTERIZATION AND APPLICATION IN FLOW-INJECTION DETERMINATION OF CARBOHYDRATES AND AMINO-ACIDS

A novel Eastman-AQ/Ni(II) chemically modified electrode (CME) produced by "double coating step" deposition of a poly(ester sulphonic acid) polymer film and Ni2+-containing crystalline species onto glassy carbon instead of a metallic nickel electrode exhibited stable electrocatalytic oxidation of numerous alpha-hydrogen compounds including carbohydrates, amines and amino acids. In cyclic voltammetry, the electrocatalysis appeared with an irreversible anodic wave at +0.55 V (vs. Ag/AgCl). The CME was adapted for constant-potential amperometric detection of these compounds in flow injection analysis. Using the CME, the linear response concentration range was between 1.0 x 10(-5) and 5.0 x 10(-2) mol/l and the detection limit was 5.0 x 10(-6) mol/l for glucose. The stability of the CME was adequate for routine quantitative application.

DETERMINATION OF THE MARK-HOUWINK EQUATION FOR CHITOSANS WITH DIFFERENT DEGREES OF DEACETYLATION

The values of k and alpha in the Mark-Houwink equation have been determined for chitosans with different degrees of deacetylation (DD) (69, 84, 91 and 100% respectively), in 0.2 M CH3COOH/0.1 M CH3COONa aqueous solution at 30-degrees-C by the light scattering method. It was shown that the values of alpha-decreased from 1.12 to 0.81 and the values of k increased from 0.104 x 10(-3) to 16.80 x 10(-3) ml/g, when the DD varied from 69 to 100%. This is due to a reduction of rigidity of the molecular chain and an increase of the electrostatic repulsion force of the ionic groups along the polyelectrolyte chain in chitosan solution, when the DD of chitosan increases gradually.