Determination of zinc in marine/lacustrine sediments by graphite furnace atomic absorption spectrometry using Pd/Mg chemical modifier and slurry sampling

Effectiveness of Pd/Mg chemical modifier for the accurate direct determination of zinc in marine/lacustrine sediments by graphite furnace atomic absorption spectrometry (GF-AAS) using slurry samples was evaluated. A calibration curve prepared by aqueous zinc standard solution with addition of Pd/Mg chemical modifier is used to determine the zinc concentration in the sediment. The accuracy of the proposed method was confirmed using Certified Reference Materials, NMIJ CRM 7303-a (lacustrine sediment) from National Metrology Institute of Japan, National Institute of Advanced Industrial Science and Technology, Japan, and MESS-3 (marine sediment) and PACS-2 (marine sediment) from National Research Council, Canada. The analytical results obtained by employing Pd/Mg modifier are in good agreement with the certified values of all the reference sediment materials. Although for NRC MESS-3 an accurate determination of zinc is achieved even without the chemical modifier, the use of Pd/Mg chemical modifier is recommended as it leads to establishment of a reliable and accurate direct analytical method. One quantitative analysis takes less than 15 minutes after we obtain dried sediment samples, which is several tens of times faster than conventional analytical methods using acid digested sample solutions. The detection limits are 0.13?µg?g^?1 (213.9?nm) and 16?µg?g^?1 (307.6?nm), respectively, in sediment samples, when 40?mg of dried powdered samples are suspended in 20?mL of 0.1?mol?L^?1 nitric acid and a 10?µl portion of the slurry sample is measured. The precision of the proposed method is 8–15% (RSD).     

Phase Systems and Post-Column Dithizone Reaction Detection for the Analysis of Organo-Mercurials by HPLC

Abstract

The suitability of HPLC (normal and reversed phase adsorption) with UV or post-column reaction detection for the analysis of organomercurials was investigated systematically. The separation of organomercurials is best carried out on a reversed phase system with a C-8 bonded phase material as the stationary phase and acetonitrile-aqueous sodium bromide mixtures as the mobile phase.

The precision and detection limit of the method and the efficiency of the extraction procedure were established. For the alkylmercury compounds the lowest limit of detection (80ppb) was obtained with the dithizone reaction detection and for the phenylmercury compounds with UV detection (60ppb). A chromatogram of a spiked fish (2ppmHg) and a river water sample (50ppbHg) is shown.     

Formation of Quaternary Stereogenic Centers by Copper‐Catalyzed Asymmetric Conjugate Addition Reactions of Alkenylaluminums to Trisubstituted Enones

Alkenylaluminums undergo asymmetric copper‐catalyzed conjugate addition (ACA) to β‐substituted enones allowing the formation of stereogenic all‐carbon quaternary centers. Phosphinamine–copper complexes proved to be particularly active and selective compared with phosphoramidite ligands. After extensive optimization, high enantioselectivities (up to 96 % ee) were obtained for the addition of alkenylalanes to β‐substituted enones. Two strategies for the generation of the requisite alkenylaluminums were explored allowing for the introduction of aryl‐ and alkyl‐substituted alkenyl nucleophiles. Moreover, alkyl‐substituted phosphinamine (SimplePhos) ligands were identified for the first time as highly efficient ligands for the Cu‐catalyzed ACA.     

Enthalpy–Entropy Compensation Combined with Cohesive Free‐Energy Densities for Tuning the Melting Temperatures of Cyanobiphenyl Derivatives

This work illustrates how minor structural perturbations produced by methylation of 4′‐(dodecyloxy)‐4‐cyanobiphenyl leads to enthalpy–entropy compensation for their melting processes, a trend which can be analyzed within the frame of a simple intermolecular cohesive model. The transformation of the melting thermodynamic parameters collected at variable temperatures into cohesive free‐energy densities expressed at a common reference temperature results in a novel linear correlation, from which melting temperatures can be simply predicted from molecular volumes.     

Selective Dimerization of Lewis‐Acid/Base‐Stabilized Phosphanylalanes

The reaction of [{(CO)₅W}PRH₂] (R=H, Ph) with H₃Al ? NR₃ (R=Et, Me) leads to the formation of four‐membered heterocyclic compounds [({(CO)₅W}P(H)AlH ? NEt₃)₂] and [({(CO)₅W}PhPAlH ? NMe₃)₂]. Upon dissolving the solid compounds, fast equilibria between the isomers are observed on the NMR timescale. Further insight into the stability and reactivity of the isomers was gained by applying theoretical methods. DFT calculations predict that hydrogen elimination in the case of [({(CO)₅W}PhPAlH ? NMe₃)₂] may be reversible.     

Reaction of a Dialumene‐Benzene Adduct with Diphenylacetylene: Formation of 3,4‐Dialuminacyclobutene and 5,6‐Dialuminabicyclo[2.1.1]hex‐2‐ene Derivatives

Reaction of a dialumene‐benzene adduct bearing bulky aryl substituents with diphenylacetylene was found to give a novel 5,6‐dialuminabicyclo[2.1.1]hex‐2‐ene derivative in addition to the 3,4‐dialuminacyclobutene derivative, the formal [2+2]cycloadduct of an intermediary dialumene with diphenylacetylene. The molecular structure of the newly obtained 5,6‐dialuminabicyclo[2.1.1]hex‐2‐ene has been elucidated by X‐ray crystallographic analysis.     

The Research of Sulfuric Acidic Recycling of Aluminum Industry Fluorine-containing Waste Products

The article presents the method of recycling aluminum industry fluorine-containing waste products to produce hydrogen fluoride. We carried out the estimate of the thermodynamic parameters of sulfuric acidic recycling of fluorine-containing waste products. We considered the necessity of waste products preliminary oxidizing roast stage to reduce carbonic constituent due to the interaction between carbonic constituent blocks of the sulfuric acid and waste products. We also carried out the researches for kinetic characteristics and to determine the optimal conditions for the to recycle sulfuric acidic in the fluorine-containing waste products.     

航空铝合金预腐蚀疲劳寿命退化规律

航空铝合金材料在服役过程中常因腐蚀损伤而导致疲劳断裂问题,通过采用扫描电镜及疲劳寿命测试等方法,研究了不同预腐蚀损伤对2xxx铝合金在不同应力比下疲劳寿命的影响,探讨了预腐蚀损伤对疲劳裂纹萌生扩展的影响机理.结果表明:预腐蚀损伤对2xxx铝合金材料疲劳寿命的影响显著,材料的疲劳性能随着腐蚀损伤程度的增加而明显下降.同时建立了预腐蚀损伤对材料疲劳极限的影响系数C-T-R模型,材料疲劳极限的影响系数C随着预腐蚀时间的增加或者应力比R的增加而变大.断口分析表明,预腐蚀损伤的存在导致裂纹萌生寿命大大缩短,裂纹萌生由单源转变为多源,并且均萌生于腐蚀坑处.     

基于气基直接还原-熔分的硼铁矿高效利用新工艺

实验室条件下,以含硼铁精矿为原料制备氧化球团,对含硼铁精矿气基竖炉直接还原-电炉熔分新工艺进行了研究.结果表明,含硼铁精矿是良好的造球原料,1 200℃下焙烧20 min后,成品球团抗压强度可达2 500 N以上,满足气基竖炉直接还原工艺要求.在H2与CO体积比大于2/5且温度在850~1 000℃条件下,含硼铁精矿氧化球团还原率达到95%的时间为15~60 min,还原膨胀率不高于15%.在高温下电热熔化DRI后硼和铁可以高效分离,硼、铁收得率均可达到98%以上,富硼渣中B2O3的质量分数在21%以上,活性可达89%左右,是"一步法"生产硼酸的优良原料.含硼铁精矿气基竖炉直接还原电炉熔分新工艺可以实现硼铁高效分离和清洁利用.     

成形速度对7075半固态模锻组织均匀性的影响

在半固态模锻过程中,经常会出现液相偏析现象,使零件出现"弱点"或"弱区",这些"弱点"或"弱区"通常又是潜在的裂纹源和服役条件下失效的起因。为了分析研究半固态模锻液相偏析的影响因素,应用DEFORM-3D软件对7075铝合金半固态模锻充型过程进行了模拟,研究了成形速度对7075铝合金杯形件充型过程的影响规律。在模拟的基础上,利用压力机及杯形实验模具,进行了半固态7075铝合金流变模锻成形,研究了成形速度对7075铝合金杯形件半固态模锻组织均匀性的影响。模拟和实验结果表明:成形速度越高,充型越不平稳;在压头温度400℃、成形比压50 MPa、合金温度628℃的条件下,随着成形速度的增加,杯形件的液相偏析度增加,组织越不均匀,当成形速度为5mm/s时,杯形件的液相偏析度高达18.2%。