Determination of hydroxylamine by capillary electrophoresis electrochemical detection with a palladium-particle modified carbon fiber microdisk array electrode

A highly dispersed ultramicro palladium-particle modified carbon fiber microdisk array electrode (Pd-CFE) was employed for capillary electrophoresis-electrochemical (CEEC) detection of hydroxylamine (HA). The Pd particles obtained were in the nanometer scale, had a high electrocatalytic activity towards HA and exhibited good reproducibility and stability. A linear relationship between the current and the analyte concentration was found between 5 x 10(-6) and 1 x 10(-3) mol/l of HA with a correlation coefficient of 0.9992. The detection limit was 5 x 10(-8) mol/l. The applicability of the method for the determination of HA in river water and waste water was investigated.

Detection of hydrazine, methylhydrazine, and isoniazid by capillary electrophoresis with a palladium modified microdisk array electrode

A palladium particle-modified carbon fiber microdisk array electrode was designed and employed in capillary electrophoresis for the simultaneous detection of hydrazine, methylhydrazine, and isoniazid. The Pd-modified microdisk electrode had high catalytic ability for hydrazines and exhibited good reproducibility and stability. The response for hydrazine was linear over 3 orders of magnitude with a correlation coefficient of 0.993. The detection limits far hydrazine, methylhydrazine, and isoniazid were 1.2, 2.1, and 6.2 pg, respectively.

The electrochemical behavior of Eastman AQ/meldola blue-coated microelectrodes

Eastman-AQ 55D was coated onto a carbon fiber microelectrode surface, and the resulting modified electrodes exhibited high stability. Substantial improvement in the stability was observed as a result of good adhesion and the strong binding of large hydrophobic cations of Eastman AQ 55D. The electrode reaction of meldola blue bound in the polymer film showed a reversible, one-electron transfer process. The effects of solution pH and influence of supporting electrolyte on the modified carbon fiber microelectrode are discussed. The diffusion coefficient of meldola blue in the AQ polymer film determined by chronoamperometry is 2.3 x 10(-18) cm(2) s(-1), and the heterogeneous rate constant of meldola blue at the AQ polymer film/electrode determined by normal pulse voltammetry is 3.97 x 10(-3) cms(-1).

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.

UNSTEADY DIFFUSION KINETICS OF ZIEGLER-NATTA HETEROGENEOUS CATALYST POLYMERIZATION .4. PREDICTION OF EXPERIMENTAL RESULTS OF PROPYLENE ETHYLENE 1-HEXADECENE TERPOLYMERIZATION

The prediction, based on unsteady diffusion kinetics, of the enhancement of reactivity and incorporation of 1-hexadecene in its copolymerization with propylene on adding a small amount of ethylene (increase from 5,2 mol-% to 10,8 mol-% when 2% of ethylene was added, and to 16,1 mol-% when 5% was added) was verified in the terpolymerization of propylene/1-hexadecene/ethylene on a commercial Solvay-type delta-TiCl3 catalyst. The catalyst efficiency was thus also increased. These augmentations originate from the increase in diffusion coefficient of 1-hexadecene at the catalyst surface when the PP crystallinity decreases on introduction of ethylene. Calculation based on unsteady diffusion kinetics showed that the order of diffusion coefficients ethylene > propylene > 1-hexadecene is reversed as the monomer concentration increases when the monomers are not at their equilibrium concentration. Sequence distribution as determined by means of C-13 NMR revealed a tendency of blocky structure rather than a Bernoullian one. The terpolymer compositions obtained by means of an IR method developed in this work conform rather well with the NMR results. Results in this work not only support the unsteady diffusion kinetics but also provide a new route to prepare olefinic copolymer rubbers with heterogeneous titanium catalysts.

THE EFFECT OF RADIATION-INDUCED CROSS-LINKING ON THE RELAXATION OF TAUT TIE MOLECULES DURING ANNEALING OF DRAWN LDPE

Shrinkage, retractive stress, and infrared dichroism of the drawn low-density polyethylene (LDPE) as-drawn and irradiated by Co-60-ray have been measured under different annealing conditions. The shrinkage and the disorientation of the irradiated sample was undergone more rapidly than that of unirradiated one as the temperature was continuously increased, surpassing a certain value, and a higher degree of shrinkage and disorientation was achieved finally for the irradiated sample when the samples were annealed with free ends. For the samples heated isothermally with fixed ends, the retractive stress went through a maximum and then attenuated to a limited value, and the degree of such a stress attenuation for the unirradiated sample was much more than that for the irradiated sample. These results show that the taut tie molecules (TTMs) in drawn PE can relax by the pulling of chain segments out of crystal blocks that they anchored in at elevated temperatures higher than the a transition and also by the displacing of microfibrils if the samples were annealed with free ends. The cross-links produced by irradiation prohibit the former process. It was further observed that the dependence of the average extinction coefficient of the band at 2016 cm-1 on that of the band at 1894 cm-1 is related to irradiation and annealing conditions, which has also been explained by the relaxation of TTMs and the function of irradiation-induced cross-linking on the relaxation.

EVALUATION OF THE RELIABILITY OF KALMAN FILTERING RESULTS IN INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION-SPECTROMETRY

This paper deals with the evaluation of the reliability of the analytical results obtained by Kalman filtering. Two criteria for evaluation were compared: one is based on the autocorrelation analysis of the innovation sequence, the so-called NAC criterion; the other is the innovations number, which actually is the autocorrelation coefficient of the innovation sequence at the initial wavelength. Both criteria allow compensation for the wavelength positioning errors in spectral scans, but there exists a difference in the way they work. The NAC criterion can provide information about the reliability of an individual result, which is very useful for the indication of unmodelled emissions, while the innovations number should be incorporated with the normalization of the innovations or seek the help of the sequence itself for the same purpose. The major limitation of the NAC criterion is that it does not allow the theoretical modelling of continuous backgrounds, which, however, is convenient in practical analysis and can be taken with the innovations number criterion.

THE OPTICAL AND ELECTRICAL-PROPERTIES OF DYSPROSIUM AND YTTERBIUM MONOPHOSPHIDES

Dysprosium and ytterbium monophosphides have been prepared by the solid state reaction. The optical and electrical properties have been studied. Evidence that DyP and YbP are semiconductors has been obtained from the study of the absorption spectrum, the negative temperature coefficient of resistance and the rectifying effect. Their energy gaps are determined as 1.15 eV for DyP and 1.30 eV for YbP, electric conduction type is n-type, resistivities are about 10(-2) ohm cm and Hall mobility is 8.5-80 cm2/Vs. The p-n junction is formed on the LnP/Si.

STUDY ON DEPOSITION POTENTIALS OF LITHIUM AND SODIUM-IONS AND DEPOLARIZATION IN BINARY CHLORIDE

Deposition potentials of Lithium and Sodium ions have been measured in binary chloride systems (LiCl-KCl, NaCl-KCl) by I-V curve method, to provide a theoretical base for preparing high purity Al-Li alloy by electrolysis in molten salt. The changes of free energy and enthalpy were calculated in terms of depolarization values on Al cathode. Thermodynamic meaning of depolarization was discussed in details and the empirical relation between binary alloy type and depolarization type was proposed. It is shown for the first time that the presence of a third element in Al-Li alloy can strengthen depolarization of Li ion at Al alloy cathode and give foundation for preparing high purity Al-Li-M ternary alloy. The effect of LiCl concentration on deposition potentials of Li ion at Al cathode in KCl-LiCl melt was studied and average active coefficient of LiCl was obtained.

Distribution of the nonlinear random ocean wave period

Because of the intrinsic difficulty in determining distributions for wave periods, previous studies on wave period distribution models have not taken nonlinearity into account and have not performed well in terms of describing and statistically analyzing the probability density distribution of ocean waves. In this study, a statistical model of random waves is developed using Stokes wave theory of water wave dynamics. In addition, a new nonlinear probability distribution function for the wave period is presented with the parameters of spectral density width and nonlinear wave steepness, which is more reasonable as a physical mechanism. The magnitude of wave steepness determines the intensity of the nonlinear effect, while the spectral width only changes the energy distribution. The wave steepness is found to be an important parameter in terms of not only dynamics but also statistics. The value of wave steepness reflects the degree that the wave period distribution skews from the Cauchy distribution, and it also describes the variation in the distribution function, which resembles that of the wave surface elevation distribution and wave height distribution. We found that the distribution curves skew leftward and upward as the wave steepness increases. The wave period observations for the SZFII-1 buoy, made off the coast of Weihai (37A degrees 27.6' N, 122A degrees 15.1' E), China, are used to verify the new distribution. The coefficient of the correlation between the new distribution and the buoy data at different spectral widths (nu=0.3-0.5) is within the range of 0.968 6 to 0.991 7. In addition, the Longuet-Higgins (1975) and Sun (1988) distributions and the new distribution presented in this work are compared. The validations and comparisons indicate that the new nonlinear probability density distribution fits the buoy measurements better than the Longuet-Higgins and Sun distributions do. We believe that adoption of the new wave period distribution would improve traditional statistical wave theory.

Mean sea surface heights of the South and East China Seas from ocean circulation model and geodetic leveling

The mean sea surface heights (sea surface topography) of the South China, East China, Yellow and Bohai Seas are derived from an ocean general circulation model and surface air pressure. The circulation model covers the global oceans, with fine grid (1/6degrees) covering the East Asian marginal seas and coarse grid (31) covering the rest part of the global oceans. The result shows that the China 1985 National Altitude Datum is 24.7 cm above the me-an sea surface height of the world oceans. The mean sea surface in the coastal ocean adjacent to China is higher in the south than in the north. Intercomparison of the model results with the geodetic leveling measurements at 28 coastal tidal stations shows a standard deviation of 4.8 cm and a fitting coefficient of 95.3%. After correction through linear regression, the standard deviation is reduced to 4.5 cm. This indicates that the accuracy of model results is sufficient for practical application. Based on the model results, the mean sea surface heights for the study area with a resolution of 1/6 degree are given. This result also links the mean sea levels at islands with those on the mainland coast and gives the mean sea surface heights at tidal stations in the Taiwan Island, the Dongsha Islands, the Yisha Islands and the Nansha Islands relative to the China 1985 National Altitude Datum.

Observations of Kuroshio intrusion into the South China Sea

To discuss the intrusion of the Kuroshio into the SCS, we examined the mixing between the North Pacific and South China Sea (SCS) waters based on in-situ CTD data collected in August and September 2008 and the moored ADCP data taken from mid September 2008 to early July 2009. The CTD survey included four meridional sections from 119A degrees E to 122A degrees E around the Luzon Strait, during which pressure, temperature, and salinity were measured. The CTD data show that the isopycnal surface tilted from the SCS to the North Pacific; and it was steeper in the lower layers than in the upper ones. Meanwhile, we found strong vertical mixing taken place in the areas near 121A degrees E. The Kuroshio in high temperature and salinity intruded westward through Luzon Strait. The frequency of buoyancy was one order of magnitude greater than that of the common ones in the ocean, suggesting stronger stratification in the northeastern SCS. On the other hand, the long-term ADCP data show that before late October 2008, the direction of water flow in the SCS was eastward, and from November 2008 to late February 2009, it turned northwestward in the layers shallower than 150 m, while remained unchanged in deep layers from 200 to 450 m. From March to June 2009, the direction shifted with increasing depth from northward to southward, akin to the Ekman spiral. EOF analysis of the current time series revealed dominant empirical modes: the first mode corresponded to the mean current and showed that the Kuroshio intrusion occurred in the upper layers only from late December to early March. The temporal coefficient of the first and the second mode indicated clearly a dominant signal in a quasi-seasonal cycle.

Characteristics of nitrogen forms in the southern Huanghai Sea surface sediments

The distributions of different forms of nitrogen in the surface sediments of the southern Huanghai Sea are different and affected by various factors. The contents of IEF-N, SOEF-N and TN gradually decrease eastward, and those of SAEF-N northward, while those of WAEF-N westward. Around the seaport of the old Huanghe (Yellow) River, the contents of both SOEF-N and TN are the highest. Among all the factors, the content of fine sediment is the predominant factor to affect the distributions of different forms of nitrogen. The contents of IEF-N, SOEF-N, and TN have visibly positive correlation with the content of fine sediments, and the correlative coefficient is 0.68, 0.58 and 0.71 respectively, showing that the contents of the three forms of nitrogen increase with those of fine sediments. The content of WAEF-N is related to that of fine sediments to a certain extent, with a correlative coefficient of 0.35; while the content of SAEF-N is not related to that of fine sediments, showing that the content of SAEF-N is not controlled by fine grain-size fractions of sediments. In addition, the distributions of different forms of nitrogen are also interacted one another, and the contents of IEF-N and SOEF-N are obviously affected by TN, while those of inorganic nitrogen (WAEF-N, SAEF-N and IEF-N) are not affected by SOEF-N and TN obviously, although they are interacted each other.

Identification of factors affecting the growth and survival of the settling Japanese flounder larvae, Paralichthys olivaceus

A series of experiments were conducted to identify the factors that affected the growth and survival of the settling flounder larvae Paralichthys olivaceus. Settling larvae 24 days after hatching (DAH) were reared in 10-l experimental tanks up to 40 DAH, and two of the following factors were changed as controlled factors in each experiment: light regime (24L:0D or 12L:12D), prey density (1500, 3000, or 5000 Artemia l(-1)), shelter (sand or no sand) and stocking density (5, 10, or 15 fish l(-1)). Early settling larvae (24-35 DAH) experienced little mortality (less than 10% of the overall mortality) that was not significantly affected by above factors. In contrast, late settling larvae (36-40 DAH) suffered high cannibalistic mortality which was significantly influenced by each of the above factors. Larvae experienced significantly lower mortality at 10 fish l(-1) level than at other densities. Larvae at 15 fish l(-1) level had higher mortality than at 5 fish l(-1) when all other factors were identical. Larvae at 3000 and 5000 Artemia l(-1) treatments survived significantly better than at 1500 Artemia l(-1), but no significant differences in larval mortality were found between the two higher densities. Larvae suffered higher mortality at low prey density or at the absence of sand when they were exposed to longer photoperiod. Low stocking density significantly improved the growth of the settling larvae. The average daily instantaneous growth rate (G) at 5 and 15 fish l(-1) treatments were 0.050 and 0.034, with the coefficient of variation (CV) in final length at 16.4 and 23.5, respectively. Daily instantaneous growth rate increased significantly from 0.033 in the 1500 Artemia l(-1) to 0.041 and 0.045 in the 3000 and 5000 Artennia l(-1), respectively, but no significant difference in larval growth existed between the two higher prey densities. These findings suggested that the optimal prey density for growth and survival of the settling flounder larvae at a stocking density of 5 - 15 fish l(-1) was around 3000 Artemia l(-1) . Larvae that were exposed to 24L showed 20% increase in growth ( G = 0.046, CV = 18.7) than those exposed to 12L ( G = 0.037, CV = 20.5). Longer exposure to light significantly improved larval growth, provided sufficient food was available. Sand substrate did not show significant effects on larval growth, possibly because the larvae spent most of the time swimming or feeding in the water column during this stage. (C) 2003 Elsevier Science B.V. All rights reserved.

Simultaneous Determination of Multi-Organotin Compounds in Seawater by Liquid-Liquid Extraction-High Performance Liquid Chromatography-Inductively Coupled Plasma Mass Spectrometry

The hyphenated technique of high performance liquid chromatography coupled with inductively coupled plasma mass spectrometry (HPLC-ICP-MS) was applied to the simultaneous determination of five organotin compounds (trimethyltin, dibutyltin, tributyltin, diphenyltin and triphenyltin) in seawater samples. Agilent TC-C18 column was used for the separation, the mobile phase of HPLC was CH3CN : H2O: CH3COOH=65 : 23 : 12 (phi), 0.05% TEA, and pH value was adjusted to 3.0 by diluent ammonia. The flow rate was 0.6 mL . min(-1). Five mixed organotin compounds in a mix standard solution from 100 to 0.5 mu g . L-1 were applied for the method assessment. The experimental results indicate that the correlation coefficient of calibration curves (R-2) for each organotin compound was over 0.998 and the detection limits of the five organotin compounds were lower than 3 ng . L-1. Different mixed organic solvents including dichloromethane or toluene were used for extraction of organotin and the extraction condition of organotin from seawater was optimized. The 100 mL seawater acidized by hydrochloric acid was extracted by 10 mL carbon dichloride (CH2Cl2) with 2% tropolone for 10 min twice. Extracted organic solvents were mixed And blown to one drop by nitrogen with the rate of 1.7 mL . min(-1), then 1 mL acetonitrile was added to the drop for redissolving the organotin compounds. Finally, the mixed redissolution was filtered by 0.22 mu m organic filter membrane before analysis. it was found that the only organotin compound in seawater was triphenyltin (TPHT) and the content was 53.2 ng . L-1. The recoveries test from the standard addition for diphenyltin (DPHT), dibutyltin (DBT), tributyltin (TBT) and triphenyltin (TPHT) were over 80%. However, the recovery for trimethyltin (TMT) was relatively low and the value was 50%. The reason might be attributed to the decomposition or adsorption of those compounds during the extraction procedure. Further study on this subject is in progress.