Selective vapor phase hydroformylation of ethylene over cluster-derived cobalt catalyst

Vapor phase hydroformylation of ethylene was studied with silica-supported metal catalysts. A cobalt metal catalyst derived from Co₂(CO)₈ gave propanal and its derivatives in as high selectivity of about 36% as Rh/SiO₂ catalyst under the reaction conditions of 1.1 MPa of a gas-mixture of ArCOC₂H₄H₂ = 1333 at 423–503 K. On the other hand, conventional cobalt catalysts derived from cobalt nitrate, chloride, or acetate, and other noble metal catalysts (Pd/SiO₂ and Ir/SiO₂) produced mainly ethane.     

Determination of seventeen pesticide residues in agricultural products by LC/MS

Residues of 17 pesticides in agricultural products were determined by LC/MS with an atmospheric pressure chemical ionization (APCI) interface in both positive and negative ion modes. Pesticides were extracted with acetonitrile, and the extracts were cleaned-up with a primary and secondary amine (PSA) mini-column eluted with acetone-hexane (1:1). Rice, orange and potato were spiked with the 17 pesticides at 0.1 microgram/g and analyzed by the proposed method. The average recoveries of these pesticides usually ranged from 70 to 98% and the relative standard deviations were usually around 10%. These results suggested that LC/MS with APCI could be used to determine the residue levels of the 17 pesticides in these crops.     

Determination of free fatty acids in milk and dairy products by reversed-phase HPLC with fluorescence detection

A highly sensitive HPLC with fluorescence detection was developed for the determination of free fatty acids (FFAs) in milk and dairy products. For this purpose, the FFAs were extracted from small amounts of milk (1.0 mL), cheese (0.5 g) and butter (0.5 g) using Sep-Pak cartridge columns, and then derivatized to 9-anthrylmethyl esters with 9-anthryldiazomethane (ADAM). Good separations of the ADAM derivatives of 16 FFAs (C4-C18) that exist in milk, cheese and butter, which permitted quantitative estimation of their individual FFAs, were achieved by HPLC on a C18 column (Cadenza CD-C18, 150 x 3 mm i.d.) using gradient elution with methanol and water. The acid values calculated from the contents of individual FFAs were in good agreement with those obtained by the conventional titration method. These results demonstrate that the present HPLC method is simple, sensitive and precise, and could be utilized widely for determination of the FFAs in milk and dairy products.     

Infrared sea surface emissivity including multiple reflection effect for isotropic Gaussian slope distribution model

A method is described for incorporating surface-emitted surface-reflected (SESR) radiation into the calculation of infrared sea surface emissivity. Firstly, the direct emissivity is obtained by ignoring SESR emission. Next, the first order SESR emissivity is obtained by using the direct emission as a radiation source. Finally, the ith order SESR emissivity is iteratively obtained by using the i − 1st order SESR emission.Computational results are in good agreement with a Monte Carlo calculation, where the SESR emissivity increases from an emission angle of 50° showing a maximum value of about 0.03 at an emission angle of 80°. The direct emissivity is smaller than the measured emissivity by 0.02∼0.03 around a wavelength of 10 μm at an emission angle of 73.5°. By incorporating the SESR emission into the emissivity model, the discrepancy between the computed and the measured emissivity is significantly reduced.The advantage of the present method over the previous works is that we need not to specify a cutoff angle to differentiate the radiation from the sea and that from the sky for calculating SESR emission. Instead of using a cutoff angle, the probability that radiation originates from the sea is derived from the probability distribution function of sea surface slope. As a result, the uncertainty in the computation of sea surface emissivity attributed to the uncertainty in cutoff angle could be effectively suppressed.     

The measurement of hydrogen activities in molten copper using an oxide protonic conductor

We have developed a hydrogen sensor for in situ measurements of hydrogen activities in molten copper. The sensor consists of a concentration cell utilizing a proton conductor, CaZr_0.9In_0.1O_3-δ, as the solid electrolyte. The electromotive force (emf) of the cell was generated by both hydrogen and oxygen activity gradients across the cell in a high-temperature region simulating the fire refining processes of copper. However, accurate hydrogen activity in molten copper could be evaluated from the emf if oxygen activity in molten copper was determined simultaneously by another concentration cell and if the hydrogen and the oxygen activities at the reference electrode were known. The performance of the sensor was studied under various conditions. The observed good response and reliability of the sensor show that it should be a powerful tool for improvement of the fire refining process of the molten copper. Theoretical treatment of the calculation of the emf of the concentration cells using a mixed ionic conductor, i.e., protonic and oxide ionic conductor, as solid electrolytes is also discussed briefly.     

Microstructure and anodic polarization behavior of experimental Ag–18Cu–15Pd–12Au alloy in aqueous sulfide solution

The anodic corrosion behavior of an experimental Ag–15Pd–18Cu–12Au alloy in 0.1% Na₂S solution in relation to its microstructure was investigated using potentiodynamic and potentiostatic polarization techniques with analyses of corrosion products by X-ray diffractometry, Auger electron spectroscopy, and X-ray photoelectron spectroscopy. The role of Pd in improvement of the corrosion resistance was also investigated. In the potential/current density curve, three distinct current peaks, at –520 mV (peak I), –425 mV (peak II) and –175 mV (peak III), were observed. The Ag-rich ₂ matrix with coarse Cu and Pd-rich lamellae was the most corrosion-susceptible region, and this region was preferentially corroded at peak I with the formation of granular deposits of Ag₂S. A small amount of Ag–Cu mixed sulfide deposited on the Cu and Pd-rich coarse particles and dissolution of Ag as AgO^– might have occurred in parallel with Ag₂S formation at peak II. Enrichment of Pd on the alloy surface occurred at peak III due to preferential dissolution of Ag and Cu. A high level of corrosion resistance was attained with the formation of a thin Pd-rich sulfide film, which enhanced the passivity of the alloy in an alkaline sulfide solution. It was found that passivity is an important phenomenon not only for base metal alloys but also for noble metal alloys to maintain high levels of resistance to corrosion and tarnishing in sulfide environments.     

Investigation of gas-liquid interface in atmospheric-pressure micro plasma with solution

An atmospheric-pressure glow-discharge micro plasma in contact with liquid paraffin is stably generated by using a capacitively coupled plasma method with a mesh electrode. When characteristics of the plasma are measured in the boundary between the micro plasma (gas-phase) and liquid paraffin (liquid-phase) using optical emission spectroscopy, spectrum peaks of the emission of CH and C₂ which dissociate from paraffin are observed. The result indicates that solution can feed particles to the plasma at gas-liquid interface and this plasma is accordingly expected to promote an attractive plasma process for creating materials consisting of elements in various solutions.     

定向反射管束对辐照均匀性的影响

为使多孔陶瓷板燃气辐射器加热物体能量定向集中，减少向周围环境散失的热量，在辐射器的前方，设计了定向反射管束，并进行了被加热物体表面辐照度分布特性数值计算研究。利用蒙特卡罗法中的辐射分配因子计算并分析了相关参数，例如管束布置(顺排、叉排及节距)、加热距离、管间距及管长与半径比等对被加热物体表面辐照度均匀性的影响。通过计算得出定向反射管间距是影响均匀加热面积大小的主要因素，管束布置方式对辐照度均匀性影响较小；随管长与半径比增加，物体表面辐照度均匀时，对应的加热距离增加。计算结果为实际装置的优化设计提供了理论依据。