An application of chemometric techniques to analyze the effects of the wave function modifications on the intermolecular stretching frequencies of the hydrogen-bonded complexes

Factorial design and principal component models are used to determine how ab initio H-bond stretching frequencies depend on characteristics of the molecular orbital wave functions of acetylene–HX, ethylene–HX and cyclopropane–HX π-type hydrogen complexes with X=F, Cl, CN, NC and CCH. The results obtained for the three sets of complexes show that factorial design and principal component analyses complement each other. Factorial design calculations clearly show that these frequencies are affected mostly by inclusion of electron correlation on the calculation level. On average, their values are increased by about 25 cm⁻¹ due to a change from the Hartree–Fock (HF) to Möller–Plesset 2 (MP2) level. Valence, diffuse and polarization main effects as well as valence–diffuse, diffuse–correlation and polarization–correlation interaction effects are also important to better describe a factorial model to the H-bond stretching frequencies of these hydrogen complexes. This simplified model has been successful in reproducing the complete ab initio results, which correspond to two hundred and forty calculations. Principal component analyses applied only to hydrogen-bonded complexes whose experimental frequencies are known, has revealed that the six-dimensional original space can be accurately represented by a bidimensional space defined by two principal components. Its graphical representation reveals that the experimental intermolecular stretching frequencies are in closest agreement with the MP2/6–31+G and MP2/6–311+G ab initio results.     

Effect of Stoichiometry on Properties of Rare-Earth-Based Hydrogen Storage Alloy for Nickel-Metal Hydride Secondary Battery

Effect of stoichiometry on microstructures, electrochemical properties and PCT characteristics of the alloys MI(Ni0.71Co0.15-Al0.06Mn0.08)x (MI=Lanthanum-rich Michmetal, x=4.6~5.2) have been investigated. The lattice constants a, c, and cellvolumes of non-stoichiometric alloys are bigger than those of the stoichiometric alloy. With the increasing stoichiometry x,the value of a decreases, and the value of c and cell volume increases except for those of the stoichiometric alloy; the plateaupressure of PCT curve, discharge capacity and cycling stability all increase. The alloy with x=5.2 shows the highest dischargecapacity and the best cycling stability among the studied alloys.     

H-bond and conformations of donors and acceptors in model polyether based polyurethanes

The molecular mechanics (MM) method with COMPASS force field was used to study the H-bonds in the polyether based polyurethane model molecules. Availability of the calculation was firstly verified in comparison of some H-bonded model molecules, which were studied by using ab initio calculation, and those calculated by MM. Based on a urethane model molecule 1,3-dimethylcarbamate, which can be donor or acceptor and behaves in various conformations, it is reasonable to have a large number of H-bond interactions between various conformational donors and acceptors. For examining all the possible interaction patterns, we studied 57H-bond complexes. This systematic modeling covers well-known four types of interaction patterns, such as NH?OC (Type I), NH?O-CO (Type II), NH?NH (Type III), NH?COC (Type IV) in the system. Obtained H-bond energies were used to analyze the probabilities of the complexes. For the interaction within the hard segments, or Type I, Type II and Type III, a predominant H-bond complex has been found in the present study, which belongs to Type I. For the interaction between the hard segment and the soft segment, two conformations of Type IV were calculated to be existed.     

Inhibition effect of carbon dioxide on the oxidation of hydrogen over a platinum foil catalyst

This paper investigates the catalytic ignition of the H₂/O₂/CO₂ mixture on platinum in a stagnation flow at atmospheric pressure experimentally and numerically. We measure the ignition temperatures of the gas mixtures flowing towards resistively heated platinum with various composition ratios and various diluent gases of N₂, Ar and CO₂. Compared with N₂ or Ar, the CO₂ dilution shows higher ignition temperature by about 50 K, even at the same composition ratio. The ignition temperature increase is proportional to the dilution ratio. Through the numerical simulation, it is illustrated that higher ignition temperature is caused by the adsorption of CO₂ and following dissociation on platinum surface, which was to date considered negligible in catalytic combustion.     

The hydrogen economy, fuel cells, and electric cars

Hopes have again been raised about developing a “hydrogen economy”, in which hydrogen could be expected to replace oil and natural gas for most uses, including transportation and heating. It is again being claimed that hydrogen will be a widely available, clean, safe fuel. This article argues that such expectations are almost certainly illusory. Hydrogen, like electricity, is not an energy resource but an energy carrier. It takes more energy to extract hydrogen from water than burning the hydrogen can ever provide. There are also inevitable losses in storage, transmission, and final mechanical or heating applications. The question then turns on the efficiency—and safety—of the entire chain of conversion, from the energy source (fossil, solar, or other) to the final use. Moreover, energy sources (preferably renewable, for the long term) can be used for the direct creation of electricity, which can be introduced into the existing grid without requiring a vast investment in a new hydrogen distribution system. In addition, a hydrogen-based system would be unacceptably dangerous. This report will present a detailed technical and economic analysis of the problems with the proposed hydrogen economy and the advantages of some alternatives, principally electricity-based. A hypothetical case of what would be required for a hydrogen filling station serving the general public is closely examined.     

The magnetic structure of TbNiSiD1.78

TbNiSiD_1.78 has been studied by powder neutron diffraction below 100 K. The compound takes the hexagonal room temperature structure at 100 and 50 K (P6₃/mmc). At 2 K, below the antiferromagnetic ordering temperature of 10 K, there is a small orthorhombic distortion of the lattice. The refined unit-cell dimensions at 2 K (space group Pnma) are a=7.9505(2), b=4.02502(14), c=6.9823(2) Å. The magnetic moments of Tb are 8.71(6) μ_B, and are ordered antiferromagnetically along a.     

湿硫化氢环境下的球罐腐蚀状况分析

在湿硫化氢环境下 ,尤其储存介质中的硫化氢含量超标时 ,很容易对储存容器壳体 (含焊缝和母材 )造成硫化氢应力腐蚀或氢鼓包。作者较仔细分析了 1 0 0 0m3 丙烯球罐产生硫化氢应力腐蚀开裂和40 0m3 LPG球罐产生氢鼓包的原因。提出了此类设备在设计选材、设备制造、施工安装和使用维护等环节应注意的问题。     

宝钢研制的全氢罩式炉控制系统分析

对宝钢研制的全氢罩式炉计算机控制系统的逻辑结构、工作原理及硬件配置进行了分析.该系统与引进的系统相比,在通讯方式、程序结构、操作分析、报警和开放性等方面都有所改进.     

Development of catalysts for hydrogen generation from hydride compounds

Catalytic hydrolysis of NaBH₄ and NH₃BH₃ has been studied. It was shown that the nature of the support and the active component of the catalyst affect the H₂ generation rate. Despite similar sizes of rhodium particles formed on the surface of different supports (γ-Al₂O₃, TiO₂, carbon), their reactivity is different. Rh/TiO₂ with low rhodium concentration (1 wt.%) is the most active catalyst both in the hydrolysis of NaBH₄ and NH₃BH₃. The obtained results show that the rhodium chloride interaction with titania determines the reactivity of rhodium particles formed under action of NaBH₄ medium. TEM, DRS UV–vis and XPS were used to characterize the catalysts.     

Hydrogen production in solid electrolyte membrane reactors (SEMRs)

In the present work, the prospects and trends of solid electrolyte membrane reactors (SEMRs) towards hydrogen production, are discussed. Initially, an overview of the principles, the properties and the techniques related to the usage of the SEMRs, are presented. In the following, a literature survey covering earlier and recent developments of the various methods (e.g. reforming or partial oxidation or dehydrogenation of hydrocarbons, steam electrolysis) employed in the SEMRs for the production of hydrogen, is performed. Finally, the current status of this research field is analyzed and future research topics are proposed.