A Study on Thermal Decomposition of K_3[Fe(CN)_6] and KFe[Fe(CN)_6] in Helium

K3 [Fe(CN)6] and KFe[Fe(CN)6] are classical coordination compounds. However, the mechanism of decomposition reactions has not been well expounded. The gas products of thermal decomposition were examined by gas chroma tography (GC) , and the structure of the solid products by Mossbauer spectroscopy(MS) and X-ray diffraction(XRD). The findings are explained in terms of the theory of coordination chemistry and a decomposition mechanism is proposed in this study. On the basis of various experimental results, the first stage of the decomposition of K3[Fe(CN)6] in He was found to be the evolution of(CN)2 resulting in the reduction of Fe(Ⅲ)12K3 [Fe(CN)6]→9K4[Fe(CN)6] + Fe2 [Fe(CN)6] + 6 ( CN )For KFe [Fe(CN) 6 ], the first stage of decomposition man be represented as6KFe[Fe(CN)6]→3K2Fe[Fe(CN)6] + 2Fe2[Fe(CN)6 + 3(CN)2At higher temperatures, the decomposition of both K3[Fe(CN)6) andKFe[Fe(CN)6] to form KCN and Fe2C was accomplished by the release of(CN)2 and N2.     

火焰原子吸收光谱法研究五种螯合剂对染镉小鼠睾丸中镉钙铁锌浓度的影响

采用火焰原子吸收光谱法分别对染镉小鼠和N-对羟甲苯甲基-D-葡糖二硫代氨基甲酸钠(HBGD)、N-苯甲基-D-葡糖二硫代氨基甲酸钠(BGD)、二乙基二硫代氨基甲酸钠(DDTC)、二巯基丙醇(BAL)、乙二胺四乙酸(EDTA)等五种螯合剂治疗组小鼠睾丸中镉、钙、铁、锌等金属浓度进行了测定和研究.结果表明:镉染毒(Cd 2.5 mg·kg-1,腹腔注射)后,小鼠睾丸中镉、钙、铁、锌等金属浓度显著高于对照组(p＜0.05),染镉30 min后用各螯合剂治疗(0.400 mmol·kg-1,腹腔注射),24 h后除EDTA外,其余螯合剂能明显降低睾丸中镉的浓度并抑制钙、铁、锌浓度的增加(p＜0.05);染镉24 h后注射各螯合剂,治疗24 h后,HBGD、BGD和DDTC显著降低了小鼠睾丸中各金属浓度(p＜0.05);提示HBGD和BGD有望成为染镉中毒的理想解毒剂.     

Second derivative spectrophotometric method for simultaneous determination of cobalt, nickel and iron using 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol

A simple, sensitive and rapid derivative spectrophotometric method using 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (5-Br-PADAP) has been developed for simultaneous determination of Co(II), Ni(II) and Fe(II) which have very similar chemical behavior and appear together in many real samples. The complexes of all these metal ions with 5-Br-PADAP were formed immediately at pH 7.0 ammonium acetate buffered solution and were stable for at least 24 h. Second derivative spectra were selected for evaluation, because working wavelength determination was more precise and spectral overlap was less than in the ordinary and first derivative spectra. Three wavelengths at which the complexes exhibit extremum ²D values for Co(II), Ni(II) and Fe(II) were selected as analytical wavelengths, i.e., 640, 600 and 740 nm, respectively. Calibration curves drawn with zero-to-peak values at mentioned wavelengths were linear between 80 and 2000 ng ml⁻¹ for each metal ion. Concentrations of Co(II) and Ni(II) were calculated from the total ²D values and the sum of the linear equations for these three cations at 640 and 600 nm, after Fe(II) assay by making use of the ²D value at 740 nm. Limits of detection (LOD) for Co(II), Ni(II) and Fe(II) were 2.7, 13.9 and 3.0 ng ml⁻¹, respectively. The method has been applied to tool steel and heater resistance wire samples successfully.     

Partial Oxidation of Methane to Synthesis Gas over Hexaaluminates LaMAl11O19-δ catalysts

A series of M-substituted hexaaluminates LaMAl11O19-δ (M=Fe, Co, Ni, Mn, and Cu)were prepared and characterized by XRD, XPS, TPR and TGA techniques, respectively. They exhibited different reducibility and catalytic activity for partial oxidation of methane (POM) to synthesis gas. Among the LaMAl11O19-δ samples, LaNiAl11O19-δ showed the best catalytic activity for the topic reaction and selectivity for synthesis gas at 780 ℃ for 2 h. The conversion of CH4 was over 99.2%, and the product selectivity for both CO and H2 was above 90.3%.     

压力、温度和晶粒尺寸对Fe-N合金的合成及结构的影响

在 1× 1 0 - 3 Pa～ 4 GPa的压力和 5 80～ 930 K温度范围内 ,利用高压技术并结合机械球磨 ,研究了压力、温度和晶粒尺寸对α-Fe与非晶 BN的固态反应的影响 .发现高压和晶粒细化可以极大地促进α-Fe和非晶 BN的固态反应过程 ,α-Fe与非晶 BN发生固态反应的临界晶粒尺寸约 8nm.压力和温度对反应产物及其晶体结构有明显影响 .2 GPa和 80 0 K时 ,反应产物为具有正交结构的 Fe-N新相 ;在 3～ 4 GPa和 690～80 0 K时 ,可形成单一ε-Fex N合金相 ;而在 4 GPa和 930 K以上 ,反应产物由 Fe-N合金相转变为 Fe3B相     

Fe(0)催化三氯乙酸烯丙酯的环化反应研究

通过对Fe(O)催化烯烃自由基环化反应的研究，发现以Fe(O)为催化剂催化三氯 乙酸烯丙酯分子内自由基环化反应可以高化学选择性得到五元环内酯产物，反应中 不需加入配体。和大多数自由基反应一样，反应温度与催化剂用量对该反应的转化 率和产率有着很大的影响。     

混合稀土对ZL108铝合金组织与性能的影响

对稀土处理前后的ZL108合金进行了机械性能测试和断口分析, 表明稀土处理有利于提高合金的塑性和强度. 对稀土处理前后合金中氢总量进行了分析, 未加稀土的合金内氢总量与稀土处理后的合金相当, 结合性能与断口形态, 从侧面表明稀土改变了氢的存在形式.     

Mo/Fe3O4(111)表面对燃煤烟气汞吸附的密度泛函研究

利用CASTEP软件包采用密度泛函理论计算研究了过渡金属Mo掺杂Fe_3O_4(111)Fe_(tet)表面对Hg~0、HgCl和HgCl_2的吸附特征,分析了Mo掺杂前后Fe_3O_4(111)Fe_(tet)表面上不同汞物种的吸附形态。结果表明,Mo掺杂Fe_3O_4(111)Fe_(tet)表面对HgCl和HgCl_2为化学吸附,而对Hg~0的吸附为物理吸附;与纯净表面相比,HgCl在Mo原子掺杂表面上的吸附能提高了40%-66%。HgCl_2在纯净Fe_3O_4(111)Fe_(tet)表面形成"M"形结构;而掺杂Mo原子后,由于Cl原子与Mo原子之间更强的相互作用,使得HgCl_2发生了完全解离,两个Cl原子分别与Mo原子和Fe原子成键吸附在表面,Hg脱附。相关研究结果可为脱除燃煤烟气中的汞提供一定的理论指导。     

Iron-Cobalt-Silica Aerogel Nanocomposite Materials

Iron-Cobalt-Silica nanocomposites were prepared in form of aerogels. X-ray diffraction, transmission electron microscopy and N₂ physisorption at 77 K were used to investigate the structure, size and dispersion of the nanocrystals and the porous structure in the aerogels and in the final composites. The variation of the supercritical drying conditions gives rise to differences in the morphological features of the aerogels. These differences influence the size of the cobalt oxide nanoparticles in the aerogels. On the other hand, after the reduction treatment the average size of the alloy nanoparticles is the same in all the aerogel nanocomposites. The effect of reduction temperature on alloy formation and particle size is also discussed.     

Evaluation of digestion procedures for the determination of iron and zinc in biscuits by flame atomic absorption spectrometry

An evaluation is made of different digestion methods for the determination of iron and zinc in biscuits prior to flame atomic absorption analysis. For the initial studies, microwave digestion was enough (using hydrogen chloride and nitric acid 3:1, v/v, at 180 °C and 600 W) to provide comparable accuracy, precision, digestion time and non-critical handling of reagents to dry-ashing and wet digestion (using different acid mixtures) and also to a simple acid treatment at room temperature. Although, after a simple microwave digestion, the spiked recoveries were found around 96–102%, to reduce the digestion time and for simplicity we worked on wet acid treatments. The results showed that acid-only treatment is not enough to digest the samples without adding ethanol, which was found necessary to digest organic residue at room temperature. The method was validated by comparison of the data found for commercial biscuit samples through using the proposed procedure and the AOAC official reference spectrophotometric method. Fe concentration in the different biscuits (such as petit beurre, baby biscuits, etc.) ranged from 1.21 to 15.96 mg/100 g while Zn concentration ranged from 0.58 to 2.50 mg/100 g depending on biscuit type. The highest concentration of Fe was in baby biscuits and these biscuits were about thirteen times richer in Fe than petit beurre biscuits.