Kinetics and mechanism of Y(III) extraction with CA-100 using a constant interfacial cell with laminar flow

The Yttrium(III) extraction kinetics and mechanism with secnonylphonoxy acetic acid (CA-100) were investigated by a constant interfacial cell with laminar flow. The studies of interfacial tension and solubility of extractant and effects of the stirring rate, temperature, specific interfacial area and species concentration on the extraction rate showed that the extraction regime was dependent on the extraction conditions and the most probable reaction zone was at the liquid-liquid interface. The rate equation of extracting yttrium by CA-100 in heptane was Rf = k[Y3+]((a))[H(2)A(2)]((o))(0.88)[H+]((a))(-1.08).

Simultaneous determination of both the calibration constant in an electrochemical quartz crystal microbalance and the active surface area of a polycrystalline gold electrode

A novel method is employed for the simultaneous determination of both the calibration constant of an electrochemical quartz crystal microbalance (EQCM) and the active surface area of a polycrystalline gold electrode. A gold electrode: is immersed into a 1 mM KI/1 M H2SO4 solution and on which forms a neutral monolayer. The adsorbed iodine can then be completely oxidized into IO3-. The active surface area of a gold electrode can be obtained from the net electrolytic charge of the oxidation process, and the calibration constant in the EQCM can be calculated from the corresponding frequency shift. The result shows that this method is simple, convenient and valid. (C) 2000 Elsevier Science S.A. All rights reserved.

Comparison of different methods for variable selection

In chemistry for chemical analysis of a multi-component sample or quantitative structure-activity/property relationship (QSAR/QSPR) studies, variable selection is a key step. In this study, comparisons between different methods were performed. These methods include three classical methods such as forward selection, backward elimination and stepwise regression; orthogonal descriptors; leaps-and-bounds regression and genetic algorithm. Thirty-five nitrobenzenes were taken as the data set. From these structures quantum chemical parameters, topological indices and indicator variable were extracted as the descriptors for the comparisons of variable selections. The interesting results have been obtained. (C) 2001 Elsevier Science B.V. All rights reserved.

Variable selection by orthogonal descriptors and prediction of R-f value of phenol and aniline derivatives

Orthogonal descriptors is a viable method for variable selection, but this method strongly depend on the orthogonalisation ordering of the descriptors. In this paper, we compared the different methods used for order the descriptors. It showed that better results could be achieved with the use of backward elimination ordering. We predicted R-f value of phenol and aniline derivatives by this method, and compared it with classical algorithms such as forward selection, backward elimination, and stepwise procedure. Some interesting hints were obtained.

The kinetics study in liquid-liquid systems with constant interfacial area cell with Laminar flow

A novel constant interfacial cell with laminar flow is proposed as an approach to obtain extraction kinetics data in liquid-liquid systems. Applications and theoretical fundamentals of the apparatus have been elaborated.. The equation which can express the mass transfer of liquid-liquid system run in the constant interfacial cell with laminar flow is deduced. Simulations from the equations indicate that diffusivity is a suitable factor to represent the characteristics of extraction kinetics rather than the extraction rate in the diffusion controlling step. The dependence of the aqueous phase concentration on time is recommended to determine the extraction regime. The diffusivities of the EuCl3-HDEHP extraction system obtained by different methods are compared to certify the hydrodynamic theory of the cell. The diffusivities of the ErCl3-HEH/EHP extraction system are determined, which show that this technique is a convenient method to obtain the diffusivities in the liquid-liquid system and to determine the extraction regime. (C) 1998 Elsevier Science Ltd. All rights reserved.

Determination of the standard heterogeneous rate constant in polyelectrolyte using steady state microdisk voltammograms

The steady state voltammogram at a microdisk electrode is used to measure the diffusion coefficient and standard heterogeneous rate constant (k(s)) of ferrocene in polyelectrolyte PEG + LiClO4. The k(s) obtained is smaller in polyelectrolyte than in liquid medium. It is proposed that the polymer solvent electron transfer dynamics are affected by the relaxation rates of the ether dipole sites on the polymer chains, which are in turn constrained by the rates of polymer chain segment, or local structure, relaxations. The dependence of k(s) on temperature is observed. The k(s) increases with increasing temperature.

Tip-induced dynamic characterization of multilayers and variable morphologies of cytochrome c molecules on highly oriented pyrolytic graphite revealed by in-situ scanning tunnelling microscopy

The dynamic states of cytochrome c multilayers on electrochemically pretreated highly oriented pyrolytic graphite (HOPG) have been studied by in-situ scanning tunnelling microscopy (STM) under potential control of both the tip and the substrate in cytochrome c and phosphate buffer solution. The dynamic characterization of cytochrome c multilayers and relatively stable adsorbed single cytochrome c molecules scattered on HOPG imply that physically adsorbed multilayers were more easily influenced by the STM tip than those of chemically adsorbed single molecules. In-situ STM images of chemically adsorbed cytochrome c molecules with discernible internal structures on HOPG revealed that morphologies of cytochrome c molecules also suffered tip influence; possible tip-sample-substrate interactions have been discussed.

SYNTHESIS AND VARIABLE-TEMPERATURE FTIR STUDY OF 5 CHIRAL LIQUID-CRYSTALS INDUCED BY INTERMOLECULAR HYDROGEN-BONDING

Five new chiral liquid crystal systems induced by intermolecular hydrogen bonding between 4-[(S)-2-chloro-3-methyl]butyroyloxy-4'-stilbazole (MBSB, proton acceptor) and 4-alkoxybenzoic acids (nBA, proton donors) were prepared. Their liquid crystalline properties were investigated by DSC and polarized optical microscopy. Chiral nematic and chiral smectic phases were observed, and the thermal stability of one complex was studied through temperature dependent infrared spectroscopy.

STUDY ON ELECTROCATALYTIC OXIDATION OF NADH BY FERROCENE DERIVATIVES AND DETERMINATION OF CATALYTIC RATE-CONSTANT AT MICRODISK ELECTRODE

The electrocatalytic oxidation of NADH by ferrocene derivatives and the influence of complexation with beta-cyclodextrin (beta-CD) were investigated at a microdisk electrode in a buffer solution. The cyclic voltammetric behavior of the ferrocene derivatives on the microdisk electrode was used to determine the electron-transfer rate constant from NADH to the ferricinium species. The heterogeneous rate constants and the diffusion coefficient of ferrocene derivatives were determined with the microdisk electrode. The effect of temperature and pH on the electrocatalytic oxidation of NADH were assessed.

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.

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.

LEAST-SQUARES POLYNOMIAL SMOOTHING FOR INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION-SPECTRA

The use of least-squres polynomial smoothing in ICP-AES is discussed and a method of points insertion into spectral scanning intervals is proposed in the present paper. Optimal FWHM/SR ratio can be obtained, and distortion of smoothed spectra can be avoided by use of the recommended method.

An extended variable-grid global ocean circulation model and its preliminary results of the equatorial Pacific circulation

To investigate the interaction between the tropical Pacific and China seas a variable-grid global ocean circulation model with fine grid[(1/6)degrees] covering the area from 20degreesS to 50degreesN and from 99degrees to 150degreesE is developed. Numerical computation of the annually cyclic circulation fields is performed. The results of the annual mean zonal currents and deep to abyssal western boundary currents in the equatorial Pacific Ocean are reported. The North Equatorial Current,the North Equatorial Countercurrent, the South Equatorial Current and the Equatorial Undercurrent are fairly well simulated. The model well reproduces the northward flowing abyssal western boundary current. From the model results a lower deep western boundary current east of the Bismarck-Solomon-New Hebrides Island chain at depths around 2 000 in has been found. The model results also show that the currents in the equatorial Pacific Ocean have multi-layer structures both in zonal currents and western boundary currents, indicating that the global ocean overturning thermohaline circulation appears of multi-layer pattern.

Interbasin freshwater, heat and salt transport through the boundaries of the East and South China Seas from a variable-grid global ocean circulation model

The monthly and annual mean freshwater, heat and salt transport through the open boundaries of the South and East China Seas derived from a variable-grid global ocean circulation model is reported. The model has 1/6degrees resolution for the seas adjacent to China and 30 resolution for the global ocean. The model results are in fairly good agreement with the existing estimates based on measurements. The computation shows that the flows passing through the South China Sea contribute volume, heat and salt transport of 5.3 Sv, 0.57 PW and 184 Ggs(-1), respectively (about 1/4) to the Indonesian Throughflow, indicating that the South China Sea is an important pathway of the Pacific to Indian Ocean throughflow. The volume, heat and salt transport of the Kuroshio in the East China Sea is 25.6 Sv, 2.32 PW and 894 Ggs(-1), respectively. Less than 1/4 of this transport passes through the passage between Iriomote and Okinawa. The calculation of heat balance indicates that the South China Sea absorbs net heat flux from the sun and atmosphere with a rate of 0.08 PW, while the atmosphere gains net heat flux from the Baohai, Yellow and East China Seas with a rate of 0.05 PW.