A WOUND-TYPE LITHIUM POLYANILINE SECONDARY CELL

A wound-type cell with a polyaniline (PAn) positive electrode, a LiClO4-propylene carbonate (PC) electrolyte, and a lithium foil negative electrode has been constructed. The two electrodes are separated by a polypropylene separator. The PAn is deposited on carbon felt from a HClO4 solution containing aniline by galvanostatic or potentiostatic electrolysis. Using cyclic voltammetry charge/discharge cycles and charge/retention tests, the following results have been obtained: (i) reversibility of the charge/discharge reaction of the PAn electrode is very good; (ii) more than 50 charge/discharge cycles at 80% charge/discharge efficiency and 260 W h kg-1 discharge energy density can be achieved at 50 mA between 2 and 4 V; (iii) the open-circuit voltage and the capacity retention of the battery after storage at open-circuit for 60 days are 3.4 V and 33%, respectively.

ELECTROCHEMICAL-BEHAVIOR OF YTTRIUM ION IN LICL-KCL-NACL EUTECTIC MELT

The electrochemical reduction of yttrium ion on a molybdenum electrode in a LiCl-KCl-NaCl eutectic melt at 723 K was found to be almost reversible and to proceed by a one-step three electron reaction. The diffusion coefficient D of the Y(III) ion was measured to be (3.3 +/- 0.4) x 10(-6) cm2 s-1 by cyclic voltammetry, (5.0 +/- 0.9) x 10(-6) cm2 s-1 by the rotating disk electrode method, and (7.1 +/- 0.7) x 10(-6) cm2 s-1 by chronopotentiometry. The D values obtained by the latter two methods are in fairly good agreement with each other. The rather low D value obtained by cyclic voltammetry might be attributed to the fact that yttrium metal can dissolve slightly in the chloride melt. The standard potential of Y(III)/Y(0) couple was determined to be (-3.174 +/- 0.006) V (vs. Cl2/Cl-) by open-circuit potentiometry, (-3.15 +/- 0.02) V (vs. Cl2/Cl-) by the rotating disk electrode method and (-3.16 +/- 0.02) V (vs. Cl2/Cl) by chronopotentiometry. These three values are in good agreement with each other. Several types of Ni-Y intermetallic compounds were found to be formed on a nickel electrode.

ELECTROCHEMICAL STABILITY AND ELECTROCATALYSIS BEHAVIORS OF POLY(3-METHYLTHIOPHENE) THIN-FILM MODIFIED ELECTRODES

The Electrochemical stability of poly(3-methylthiophene) (PMT) thin film modified glassy carbon electrodes was investigated experimentally with successive cyclic voltammetry(CV) The effects of electrolyte solutions on the stability were studied. In the presence of small hydrated anions (less-than-or-equal-to 3.5nm) in the solution, the electroactivity of PMT films decreased with the characteristics of second order kinetics. In a solution with large hydrated anions (greater-than-or-equal-to 4 nm), PMT films have good stability. PMT/GO electrode can electrocatalyse the oxidation of Br- and Cl- anions, and loses its electroactivity rapidly. X-ray photoelectron spectra (XPS) have demonstrated that chlorine has bonded covalently onto the PMT structure after OV cycles in NaCl solutions.

THE TRANSFER OF METAL-IONS ACROSS THE WATER-NITROBENZENE INTERFACE FACILITATED BY NEUTRAL CARRIER ETH-129

The transfer of H+, Li+, Na+, Zn2+, Mg2+ and Cu2+ facilitated by ionophore ETH 129 (N, N, N', N'-tetracyolohexyl-3-oxapentanediamide) across water/nitrobenzene interface has been studied by the cyclic voltammetry. The mechanism of the transfer process has been discussed. The diffusion coefficients and the stability constants of the complexes formed in the nitrobenzene phase have been determined.

SPECTROELECTROCHEMICAL STUDY OF BILIRUBIN IN DIMETHYL FORMAMIDE

The electrochemical reduction of bilirubin (BR) in dimethyl formamide (DMF) is discussed in detail. The kinetic study of the electroreduction process of BR results in values of 7.94 x 10(-6) cm2/s for the diffusion coefficient and about 10(-3) cm/s for the standard heterogeneous electrode reaction rate constant. Thin-layer spectroelectrochemical investigations of BR exhibit a blue shift and a red shift at E(pc) = -0.6 V and E(pc) = -0.85 V respectively. They also give values of E0' = -1.55 V and n = 1 for the reduction process, and E0' = -1.35 V and n = 1 for the oxidation process. It was found experimentally that as the potential changes from negative to positive, the sequential color changes are similar to those of some of the color components in visible light. A mechanism for BR electroreduction in DMF has been proposed.

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.

ELECTROCATALYTIC OXIDATION OF ASCORBIC-ACID AT A PRUSSIAN BLUE FILM MODIFIED MICRODISK ELECTRODE

The preparation and the behaviour of a Prussian Blue (PB) film on a platinum microdisk electrode has been described. Electrocatalytic oxidation of ascorbic acid has occurred at the PB film modified microelectrode. This shows a typical example of a modified microelectrode in electrocatalysis following our previous theoretical studies (J. Electroanal. Chem., 309 (1991) 103) and the related catalytic reaction rate constant was determined.

ELECTROCHEMICAL STUDY OF CHOLINE DERIVATIVES TRANSFER ACROSS THE LIQUID LIQUID INTERFACE

Transfer behaviors across the water/nitrobenzene interface were studied for five choline derivatives by chronopotentiometry with linear current scanning, cyclic voltammetry and differential pulse voltammetry. The irreversible hydrolysis reactions coupled to the phase transfer of ions across the water/nitrobenzene interface were observed. The Gibbs energies of the transfer of choline derivatives show the effects of an additive constitution on hydrophobic property of the medicine.

COBALT PORPHYRIN NAFION FILM ON CARBON MICROARRAY ELECTRODE TO MONITOR OXYGEN FOR ENZYME ANALYSIS OF GLUCOSE

A microcarbon array electrode was modified by the placement of a Nafion film containing cobalt tetramethylpyridyl phorphyrin on its surface. This electrode was applied to the analysis of solution glucose when it was further modified by the immobilization of glucose oxidase on the outermost surface of the Nafion by the cross-linking of serum albumin with glutaraldehyde. The concomitant decrease in the concentration of oxygen, as it was consumed in the enzymatic reaction of glucose with glucose oxidase, was determined by either cyclic voltammetry or a double potential step method at the porphyrin-Nafion catalytic electrode. Glucose could be determined in the range of 0.01-4 mM rapidly, without interference from substances such as ascorbate or other saccharides.

ANODIC-OXIDATION OF HYDRAZINE ON GLASSY-CARBON MODIFIED BY MACROCYCLIC TRANSITION-METAL COMPLEXES .1. COBALT PROTOPORPHYRIN DIMETHYL ESTER MODIFIED ELECTRODE

The electrocatalytic oxidation of hydrazine (N2H4) on a glassy carbon electrode (GC) modified by monolayer and polymer films of cobalt protoporphyrin dimethyl ester (CoPP) has been studied. Both the monolayer and polymer films of CoPP are very active to the anodic oxidation of N2H4. The activity of CoPP for the anodic oxidation of N2H4 is dependent on the pH of the solution, and the thickness of polymerized CoPP film. The oxidation kinetics were examined by methods of cyclic voltammetry, rotating disc electrodes and steady-state polarization measurement.

FLOW-INJECTION ANALYSIS OF MYOGLOBIN AND HEMOGLOBIN AT TOLUIDINE BLUE CHEMICALLY MODIFIED ELECTRODE

Electrodeposition of the phenothiazine mediator titrant toluidine blue onto a glassy carbon substrate at an appropriate potential was used to construct a toluidine blue chemically modified electrode (CME) exhibiting electrocatalytic reduction for myoglobin and hemoglobin. The CME catalyzed the hemoprotein electroreduction at the reduction potential of the mediator molecule. When the CME as used as a detector for flow injection analysis at a constant applied potential of -0.30 V vs. a saturated calomel electrode, it gave detection limits of 20 and 50 ng (1.2 and 0.78 pmol) injected myoglobin and hemoglobin, respectively, with a dynamic linear concentration range over 2 orders of magnitude. After a brief equilibration period, the CME retained nearly 90% of its initial myoglobin response over 8 hours of continuous exposure to the flow-through system.

AMPEROMETRIC DETECTION AT A CARBON-FIBER ARRAY RING GLASSY-CARBON DISK ELECTRODE IN A WALL-JET CELL

A wall-jet cell incorporating a carbon fibre array ring/glassy-carbon disk electrode has been constructed, and characterized by the cyclic voltammetry and flow-injection techniques. The ring (composed of several microdisks) and glassy-carbon disk electrode, can be used separately for different purposes, e.g., detection in solution without a supporting electrolyte, collection/shielding detection with dual-electrode and voltammetric/amperometric detection with series dual-electrode. The electrode shows better collection and shielding effects than usual ring-disk electrode in quiescent solution and the series dual-electrode in a thin-layer flow-through cell. The detection limit at the ring electrode is comparable with that at a conventional-size electrode, and has been used in the mobile phase without a supporting electrolyte, proving to be a promising detector for normal-phase liquid chromatography.

ELECTROCHEMICAL INVESTIGATION OF LIQUID/LIQUID SYSTEMS USING VARIOUS ORGANIC SOLVENTS

The potential windows of the system water/pure solvent (W/P) and water/solvent mixtures(W/S) have been investigated by cyclic voltammetry with solvents whose dielectric constants lie between 5.87 and 34.82. In the presence of LiCI in the aqueous phase and tetrabutytammoniumtetraphenylborate(TBATPB) in the organic phase, the systems water/allyl iso-thiocyanate (W/AIT) and water/nitrobensene (W/NB) show a same wide epotential window. thermodynamic parameters of ion transfer W/AIT interface were determined. In systems of W/P and V/S the influence solvent effect on the standard gibbs energies of transfer of was discussed.

CYCLIC VOLTAMMETRIC STUDY ON THE TRANSFER MECHANISM OF ALKALI-METAL IONS ACROSS LIQUID LIQUID INTERFACE FACILITATED BY TRITON X-100

The transfer behavior of alkali motal ions K~+ and Na~+ across the interfaces of water/nitrobenzene and water/1, 2-dichloroethane facilitated by Triton X-100 is investigated by cyclic voltammetry with four electrodes. The equations of interfacial half-wave potential derived in terms of the mechanism proposed isverified by the experimental data and consistent with the practical △_0~wφ_p-pM curves.