Measurement of the effective thermal conductivity of a Mg–MgH2 packed bed with oscillating heating

The magnesium–magnesium hydride–hydrogen-system (Mg–MgH₂–H₂) offers, because of its combined hydrogen and heat storage capacity, the possibility to design hydride heat pumps and heat stores. For such industrial application systems based on cylindrically formed reactors filled with an active magnesium powder, the effective thermal conductivity limits the time in which the metal hydride alloy is charged and discharged with hydrogen. Determination of this transport coefficient is of fundamental importance for the optimum design of magnesium hydride reactors. The complex interrelation of the different transport mechanisms in a metal hydride packed bed and the hitherto undefined rule that the solid effective thermal conductivity behaves as a function of the hydrogen concentration, requires a reliable and simple-to-realize measuring method so as to determine the effective thermal conductivity of a magnesium hydride bed. In the present study, a report is given for the first time on the initiation of a measuring technique with oscillating change of temperature in a non-permeated packed bed of fine-grained material. The measurement of the effective thermal conductivity can ensue by tailoring the problem-specific mathematical result to the experimentally recorded temperature-time function. The effective thermal conductivity of the magnesium hydride bed varies between 2 and 8 W/(m K) in a temperature range of 523–653 K.     

Facile transformation of esters to nitriles

Various esters were efficiently converted into the corresponding nitriles in good yields by the treatment with sodium diisobutyl-tert-butoxyaluminium hydride (SDBBA-H), followed by treatment with molecular iodine in aq ammonia. The present one-pot method is very efficient and practical for the conversion of various aromatic and aliphatic esters into the corresponding nitriles.     

氢化铝锂一步还原β-烯胺酮合成1,3-胺基醇

β-烯胺酮类化合物是重要的有机合成砌块, 通过还原可用来合成具有广泛用途的1,3-胺基醇类化合物. 文献报道氢化铝锂还原β-烯胺酮为1,3-胺基醇, 只能采用两步还原的方法. 在四氢呋喃中采用过量的氢化铝锂于回流下将3-二甲胺基-1-芳基-2-丙烯酮高产率地一步还原为N,N-二甲基-3-羟基-3-芳基丙胺, 为该类化合物的合成提供了一个新方法.     

Sorption and desorption properties of a CaH2/MgB2/CaF2 reactive hydride composite as potential hydrogen storage material

The hydrogenation behavior of 3CaH₂+4MgB₂+CaF₂ composite was studied by manometric measurements, powder X-ray diffraction, differential scanning calorimetry and attenuated total reflection infrared spectroscopy. The maximum observed quantity of hydrogen loaded in the composite was 7.0 wt%. X-ray diffraction showed the formation of Ca(BH₄)₂ and MgH₂ after hydrogenation. The activation energy for the dehydrogenation reaction was evaluated by DSC measurements and turns out to be 162±15 kJ mol⁻¹ H₂. This value decreases due to cycling to 116±5 kJ mol⁻¹ H₂ for the third dehydrogenation step. A decrease of ca. 25–50 °C in dehydrogenation temperature was observed with cycling. Due to its high capacity and reversibility, this composite is a promising candidate as a potential hydrogen storage material.     

Comparative phytotoxicity of methylated and inorganic arsenic- and antimony species to Lemna minor, Wolffia arrhiza and Selenastrum capricornutum

The alkylation of metalloids through the transfer of methyl groups is an important factor in the biogeochemical cycling of elements like arsenic and antimony. In the environment, many different organic and inorganic forms of these elements can therefore be found in soils, sediments or organisms. Studies that compare the ecotoxicity of these different chemical species however are rare. Therefore, this study aimed to generate toxicity data on two scarcely studied organic compounds of arsenic and antimony, as well as to compare their toxicity to the inorganic species, which are studied so far to a higher extent, in order to improve the environmental effect assessment of these elements. To this purpose, bioassays were performed in which three different aquatic organisms (the floating water plants Lemna minor and Wolffia arrhiza and the green alga Selenastrum capricornutum) were exposed to a concentration series of 3 different arsenic species (sodium arsenite — As(III), sodium arsenate — As(V), and monomethylarsonous diiodide — MMAs(III)) and three different antimony species (antimony potassium tartrate hydrate — Sb(III), potassium hexahydroxoantimonate — Sb(V), trimethylantimony(V) bromide — TMSb(V). The observed effect concentrations demonstrated that the inorganic (III)- and (V)-valent species of arsenic were clearly more toxic than the corresponding antimony species. The highest overall toxicity has been shown by MMAs(III) followed by the inorganic As(III). The highest toxicity of the three tested antimony species has been observed for TMSb(V). The observed differences in effect levels stress the importance once more that speciation must not be ignored in toxicity studies.     

Rapid isolation of plutonium in environmental solid samples using sequential injection anion exchange chromatography followed by detection with inductively coupled plasma mass spectrometry

This paper reports an automated analytical method for rapid determination of plutonium isotopes (²³⁹Pu and ²⁴⁰Pu) in environmental solid extracts. Anion exchange chromatographic columns were incorporated in a sequential injection (SI) system to undertake the automated separation of plutonium from matrix and interfering elements. The analytical results most distinctly demonstrated that the crosslinkage of the anion exchanger is a key parameter controlling the separation efficiency. AG 1-×4 type resin was selected as the most suitable sorbent material for analyte separation. Investigation of column size effect upon the separation efficiency revealed that small-sized (2 mL) columns sufficed to handle up to 50 g of environmental soil samples. Under the optimum conditions, chemical yields of plutonium exceeded 90% and the decontamination factors for uranium, thorium and lead ranged from 10³ to 10⁴. The determination of plutonium isotopes in three standard/certified reference materials (IAEA-375 soil, IAEA-135 sediment and NIST-4359 seaweed) and two reference samples (Irish Sea sediment and Danish soil) revealed a good agreement with reference/certified values. The SI column-separation method is straightforward and less labor intensive as compared with batch-wise anion exchange chromatographic procedures. Besides, the automated method features low consumption of ion-exchanger and reagents for column washing and elution, with the consequent decrease in the generation of acidic waste, thus bearing green chemical credentials.     

Inverse hydrogen bonds between SiH_4 and hydrides of Na,Mg and Be

The optimized geometries of the three complexes between MeHn (Me=Na,Mg,Be;n=1 or 2) and SiH4 have been calculated at the B3LYP/6-311++g**,MP2/6-311++g(3df,3pd) and MP2/aug-cc-pvtz levels,respectively.The red-shift inverse hydrogen bonds (IHBs) based on Si-H,an electron donor,were reported.The calculated binding energies with basis set super-position error (BSSE) correction of the three complexes are-5.98,-8.65 and-3.96 kJ mol-1 (MP2/6-311++g(3df,3pd)),respectively,which agree with the results obtained via M...     

Theoretical study of the interaction between LiNH2 and HMgH

The lithium bond between HMgH and LiNH₂ has been predicted and characterized with quantum chemical calculations at the MP2/6‐311++G(d,p) level. Upon formation of the lithium bond, both the Mg? H and Li? N bonds are stretched. The Li? N bond undergoes a red shift, whereas the Mg? H bond exhibits a blue shift. The lithium‐bonded complex is controlled mainly by electrostatic and polarization interactions. The binding energy of HMgH with LiNH₂ is computed to be 12.47 kcal/mol. The binding of the two molecules is enhanced by the substitution with the methyl group in the Li acceptor, whereas it is weakened by the replacement with whether the electron‐withdrawing group such as F, Cl, CN, NC, or the electron‐donating group (OH and HN₂). A negative cooperativity is present in the ternary system of 2LiNH₂ and HMgH. The polarization interaction plays an important role in the negative cooperativity. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

Ionic conductivity in three crystalline phases of LiBH4 under pressure

The AC electrical conductivity of LiBH₄ was investigated below 2 GPa between 1 Hz and 1.6 MHz. The high-temperature phase has an ionic conductivity of up to 0.01 S cm^?1, while the low-temperature phases have conductivities two orders of magnitude lower. All phases show an Arrhenius behaviour with activation energies E _a between 0.5 and 0.7 eV, in good agreement with earlier data except for phase III, which is found to have the highest activation energy of the phases studied. The high-temperature phase has a minimum in E _a near 1 GPa, close to the triple point, correlated with a sudden change in activation volume. These features may indicate an isostructural phase transition. The conductivities of the ambient temperature phases increase temporarily by an order of magnitude after transitions between these phases, probably due to new diffusion channels via structural defects. The phase diagram agrees well with earlier results.     

氢化物AlH2自由基分子光谱辐射特征的研究

利用前一篇论文计算所得的振动频率、转动常数和配分函数,再将常温下的无转动跃迁矩平方近似为一常数并应用于高温,进一步编制程序,计算了氢化物AlH2分子001-000跃迁带不同温度段的辐射强度和吸收系数等谱带辐射特征.论文中计算的配分函数值与高斯计算及拟合值,不管是在常温还是高温下,都吻合较好,这说明构建的模型是可靠的,可以用来进一步计算谱带强度和吸收系数;从获得不同温度段的模拟光谱辐射特征图也可以看出,本文得到的谱带特征与文献一致.这对进一步研究自由基分子高温光谱的实验和理论都具有一定的参考作用.