Solute-solvent interactions with metal chelate electrolytes. Part III. Salting in of tris(acetylacetonato)cobalt(III) and benzene by aromatic and aliphatic ions

Salting effects of the metal chelate electrolytes, [Fe(phen)₃]Br₂, [Fe(bpy)₃]Br₂, [Co(phen)₃]Br₃, [Co(en)₃]Br₃, and [Co(pn)₃]Br₃ (where phen= 1,10-phenanthroline, bpy=2,2-bipridyl, en=ethylenediamine, and pn=1,2-propanediamine), as well as the tetraalkylammonium bromides (Bu₄NBr and Pr₄NBr), tetraphenylphosphonium bromide (Ph₄PBr), sodium tetraphenylborate (NaBPh₄), and sodium halides on the solubility of benzene and tris(acetylacetonato) cobalt (III) [Co(acac)₃, where acac=CH₃·CO·CH·CO·CH₃-] in water at 15, 20, 25, and 35°C were studied, and the transfer free energies of the nonelectrolytes from pure water to the electrolyte solutions were obtained. Co(acac)₃ is strongly salted in by [Fe(phen)₃]Br₂, NaBPh₄, and Ph₄PBr with large positive transfer enthalpies and entropies, weakly salted in by Bu₄NBr and Pr₄NBr with much less positive enthalpies and entropies and is salted out by the other electrolytes. The differences between salting effects of aromatic and aliphatic ions are discussed using the transfer enthalpy-entropy relation.     

Heterogeneous ceramics formed by grain boundary engineering

Two examples were selected to emphasize the potential of grain boundary engineering in the performance design of heterogeneous ceramics. Gadolinium-doped ceria-based powders were co-fired with additions of silica, and silica and lanthanum oxide, to test the silica scavenging role of lanthanum. The formation of one ionic conducting secondary phase, instead of an insulating phase, was attempted. The structural, microstructural, and electrical characterization of these samples confirmed the formation of one apatite-type lanthanum silicate-based phase and a significant enhancement of the grain boundary conductivity of these materials. One second approach addressed the formation of one mixed conductor, with electronically conductive grain boundaries, surrounding the grains of one lanthanum gallate-based electrolyte (core-shell type microstructure). Fe-doped grain boundaries were formed by selective Fe-diffusion (thermally assisted) from lanthanum ferrite screen printed layers. Combined microstructural and electrical characterization showed that the adopted solution was also effective.     

影响南丰蜜桔品质的土壤元素ICP-MS/ICP-AES分析

南丰蜜桔是原产于江西南丰的优良品种,但是品质随着种植地区的不同差异较大。文章借助ICP-MS/ICP-AES技术对江西6个不同地区,生产南丰蜜桔品质的土壤中植物的必需元素进行了分析,以期找到影响南丰蜜桔品质的土壤因素。结果显示, 品质较好的3个地区土壤中B, P, K, Mg和Ca含量均高于品质较差地区的含量,特别是B, P和K含量差异显著,而Fe, Mn, Si, Cu和Zn含量则低于品质差的地区。上述结果表明南丰蜜桔的品质主要受B, P, K, Mg和Ca控制,尤其是B, P, K影响较大;而Fe, Mn, Si, Cu和Zn对南丰蜜桔品质影响较小。所以在种植南丰蜜桔时应当适当增加B, P, K, Mg和Ca等肥料的施用量。     

贵州瓮福地区磷酸盐矿物类型的初步研究

对瓮福地区磷酸盐矿物类型进行了初步研究,结果表明,磷酸盐矿物类型主要为白云质磷质岩、磷质岩、泥质磷质岩及硅质磷质岩,属于碳氟磷灰石;发现了碳氟磷灰石的形态类型与沉积环境密切联系;内含丰富的藻类化石及其碎屑,其中有部分可重结晶结构,以细晶和微晶为主,不同形态和粒级的磷凝胶内碎屑、球粒、藻生物等颗粒与不同结构的磷质、白云质、泥质、硅质等填隙物,以多种形式构成的一系列颗粒结构磷块岩。     

Ionic conductivity studies of 49% poly(methyl methacrylate)-grafted natural rubber-based solid polymer electrolytes

The potential of 49% poly(methyl methacrylate)-grafted natural rubber (MG49) as a solid polymer electrolyte film in rechargeable batteries system were explored. The flat, thin, and flexible films were prepared by solution casting technique. The ionic conductivity was investigated by alternating current impedance spectroscopy. The highest conductivity of 2.3 × 10⁻⁷ Scm⁻¹ was obtained at 20wt.% of LiBF₄ salts content, while 4.0 × 10⁻⁸ Scm⁻¹ was obtained at 15wt.% LiClO₄ salts loading. The observation on structure performed by X-ray diffraction shows the highest conductivity appears at amorphous phase.     

ICP-AES测定红提葡萄叶片中矿质元素含量

用浓硝酸-高氯酸(4∶1)的混合溶液对红提葡萄叶片样品进行消解,采用电感耦合等离子体-原子发射光谱法(ICP-AES)测定2种不同长势的叶片样品中Zn、Ca、Mn、Fe、Mg、B和K7种矿质元素含量。各元素在实验范围内,线性关系良好,回收率为97%—103%,结果令人满意。K、Mg、Zn、Fe在长势旺盛的叶片中比长势弱的含量高,而Mn、B则相反,Ca在2种不同生长势叶片中含量相似。     

原子吸收光谱法测定冬凌草中的矿物元素

用原子吸收光谱法测定冬凌草中影响人体健康的8种矿物元素Cu、Zn、Fe、Mn、Ca、Mg、Se和Pb的含量。样品经硝酸-高氯酸消解后,采用偏振塞曼效应扣除背景吸收,用火焰原子吸收光谱法检测积分吸收测定冬凌草中Cu、Zn、Fe、Mn、Ca和Mg的含量,用石墨炉程序升温原子吸收光谱法检测峰值吸收测定Se和Pb含量。测定结果显示:该方法的精密度RSD为1.22%—5.64%;加标回收率为95.0%—110.5%;8种矿物元素的检出限(P=95%,α=0.5)分别为Cu0.034、Zn0.0028、Fe0.031、Mn0.110、Ca0.367、Mg0.132mg·mL-1,Pb1.40μg.L-1和Se1.86μg.L-1。该方法简便快速、灵敏、准确,适用于中药冬凌草中矿物元素含量的测定。     

自贡地区恐龙骨骼化石及围岩特征的研究

自贡地区恐龙化石埋藏丰富、分布广泛、保存完整,具有重要的科学价值、社会价值和经济价值。用X荧光衍射研究自贡恐龙骨骼化石及围岩元素组成,XRD结合红外光谱仪分析确定化石的矿物组成,化石切片和显微观察了解骨骼内部构造和填充物质。恐龙骨骼化石及围岩中的含钙量均较高(5%),但化石含钙量达到30%以上;化石中的含硅量较低(0.24%—1.45%),围岩中的含硅量较高(14%);化石中的含磷量为围岩的46倍以上。化石的主要化学成分是碳氟磷灰石,其次是碳酸钙;围岩的主要成分是二氧化硅。实验结果可为恐龙化石的鉴别及保护材料的研制提供理论依据。     

Phase behavior of three-component ionic fluids

We study the phase behavior of solutions consisting of positive and negative ions of valence z to which a third ionic species of valence Z>z is added. Using a discretized Debye-Hückel theory, we analyze the phase behavior of such systems for different values of the ratio . We find, for , a three-phase coexistence region and, for , a closed (reentrant) coexistence loop at high temperatures. We characterize the behavior of these ternary ionic mixtures as function of charge asymmetry and temperature, and show the complete phase diagrams for the experimentally relevant cases of and , corresponding to addition of divalent and trivalent ions to monovalent ionic fluids, respectively. Received 6 April 2000 and Received in final form 20 July 2000     

Impedance spectroscopy studies of poly (methyl methacrylate)-lithium salts polymer electrolyte systems

In the present work, five systems of samples have been prepared by the solution casting technique. These are the plasticized poly(methyl methacrylate) (PMMA-EC) system, the LiCF₃SO₃ salted-poly(methyl methacrylate) (PMMA-LiCF₃SO₃) system, the LiBF₄ salted-poly(methyl methacrylate) (PMMA-LiBF₄) system, the LiCF₃SO₃ salted-poly(methyl methacrylate) containing a fixed amount of plasticizer ([PMMA-EC]-LiCF₃SO₃) system, and the LiBF₄ salted-poly(methyl methacrylate) containing a fixed amount of plasticizer ([PMMA-EC]-LiBF₄) system. The conductivities of the films from each system are characterized by impedance spectroscopy. The room temperature conductivity in the pure PMMA sample and (PMMA-EC) system is 8.57 × 10⁻¹³ and 2.71 × 10⁻¹¹ S cm⁻¹, respectively. The room conductivity for the highest conducting sample in the (PMMA-LiCF₃SO₃), (PMMA-LiBF₄), ([PMMA-EC]-LiCF₃SO₃), and ([PMMA-EC]-LiBF₄) systems is 3.97 × 10⁻⁶, 3.66 × 10⁻⁷, 3.40 × 10⁻⁵, and 4.07 × 10⁻⁷ S cm⁻¹, respectively. The increase in conductivity is due to the increase in number of mobile ions, and decrease in conductivity is attributed to ion association. The increase and decrease in the number of ions can be implied from the dielectric constant, ɛ_r-frequency plots. The conductivity–temperature studies are carried out in the temperature range between 303 and 373 K. The results show that the conductivity is increased when the temperature is increased and obeys Arrhenius rule. The plots of loss tangent against temperature at a fixed frequency have showed a peak at 333 K for the ([PMMA-EC]-LiBF₄) system and a peak at 363 K for the ([PMM-EC]-LiCF₃SO₃) system. This peak could be attributed to β-relaxation, as the measurements were not carried out up to glass transition temperature, T _g. It may be inferred that the plasticizer EC has dissociated more LiCF₃SO₃ than LiBF₄ and shifted the loss tangent peak to a higher temperature. Paper presented at the Third International Conference on Ionic Devices (ICID 2006), Chennai, Tamilnadu, India, Dec. 7–9, 2006