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61.
62.
《Journal of Chemical Sciences》2005,117(5):525-531
The silicon atom may increase its coordination number to values greater than four, to form pentacoordinated compounds. It
has been observed experimentally that, in general, pentacoordinated compounds show greater reactivity than tetracoordinated
compounds. In this work, density functional theory is used to calculate the global softness and the condensed softness of
the silicon atom for SiH
n
F4−n
and SiH
n
F
5−n
1−
. The values obtained show that the global and condensed softness are greater in the pentacoordinated compounds than in the
tetracoordinated compounds, a result that explains the enhanced reactivity. If the results are analysed through a local version
of the hard and soft acids and bases principle, it is possible to suggest that in nucleophilic substitution reactions, soft
nucleophiles preferably react with SiH
n
F
5−n
1−
, and hard nucleophiles with SiH
n
F4−n
. 相似文献
63.
The Dantzig-Wolfe reformulation principle is presented based on the concept of generating sets. The use of generating sets allows for an easy extension to mixed integer programming. Moreover, it provides a unifying framework for viewing various column generation practices, such as relaxing or tightening the column generation subproblem and introducing stabilization techniques. 相似文献
64.
Quantitative H–Al distances in acid sites of two zeolites with MFI and IFR framework topology were obtained by numerical simulation of 1H{27Al} rotational echo adiabatic passage double resonance (REAPDOR) experiments. A 27Al offset-dependent data set yields for each resolved 1H NMR line a corresponding nuclear electric quadrupole coupling constant of the neighboring 27Al site. This information is used for analyzing a second data set for on-resonance irradiation, where the dipolar evolution time (number of rotor cycles) was varied, to yield the 1H–27Al dipolar coupling constant. Numerical simulations indicate that the REAPDOR method does not depend significantly on the polar angles, defining the orientation of the electric field gradient tensor of 27Al with respect to the Al–H dipolar vector. In contrast, the transfer of populations in double resonance sequence is sensitive to these angles, and it can be thus used to measure them. 相似文献
65.
用过氧聚钨酸(PPTA)水溶液,通过离心涂膜法在显微镜载玻片上制备了具有光滑表面且厚度为100nm的PPTA薄膜,利用PPTA薄膜在紫外光照下可研制光栅以及其它光学元件的薄膜材料,具有很高的利用价值。 相似文献
66.
Sung‐Fu Hsu Tzong‐Ming Wu Chien‐Shiun Liao 《Journal of Polymer Science.Polymer Physics》2006,44(23):3337-3347
Poly(3‐hydroxybutyrate) (PHB)/layered double hydroxides (LDHs) nanocomposites were prepared by mixing PHB and poly(ethylene glycol) phosphonates (PEOPAs)‐modified LDH (PMLDH) in chloroform solution. Both X‐ray diffraction data and TEM micrographs of PHB/PMLDH nanocomposites indicate that the PMLDHs are randomly dispersed and exfoliated into the PHB matrix. In this study, the effect of PMLDH on the isothermal crystallization behavior of PHB was investigated using a differential scanning calorimeter (DSC) and polarized optical microscopy. Isothermal crystallization results of PHB/PMLDH nanocomposites show that the addition of 2 wt % PMLDH into PHB induced more heterogeneous nucleation in the crystallization significantly increasing the crystallization rate and reducing their activation energy. By adding more PMLDH into the PHB probably causes more steric hindrance of the diffusion of PHB, reducing the transportation ability of polymer chains during crystallization, thus increasing the activation energy. The correlation among crystallization kinetics, melting behavior and crystalline structure of PHB/PMLDH nanocomposites can also be discussed. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3337–3347, 2006 相似文献
67.
J. C. Raines J. P. Schmidt J. P. Burelbach H. K. Fauske 《Journal of Thermal Analysis and Calorimetry》2006,85(1):53-55
Hydrogen
peroxide is a very versatile oxidizing agent, and it is also environmentally
compatible considering that the products of its exothermic decomposition are
oxygen and water.When kept in a clean temperature-controlled environment,
the self-reaction (decomposition) rate is extremely low. However, it is well
known that even a small amount of contamination will dramatically increase
the reaction rate. This paper describes the use of the fast thermal activity
interpreter (FTAI) instrument to examine the chemical reactivity of commercially
available 50% hydrogen peroxide at two different temperatures (30 and 40°C)
both with and without contamination. The results show that at 30°C a small
amount of rust (330 ppm) increases the reaction rate of 50% hydrogen peroxide
by a factor of 50. When the temperature is increased to 40°C, the reaction
rate is further increased by almost a factor of four. The implication for
reactivity management is that at this contamination level most practical vessel
sizes would require emergency venting capability.
An evaluation
was then performed to determine the emergency venting requirement for the
safe transportation or storage of the contaminated hydrogen peroxide. It was
determined that for quantities of the material less than 5 gallons, conventional
breather vents would be sufficient to accommodate the gas evolved. However,
for larger quantities, a safety relief device would be needed. For example,
for a 400-gallon tote bin at 40°C the required minimum vent area is estimated
to be 4.3 in2, corresponding to a minimum vent
diameter of 2.3 inches. 相似文献
68.
Methods to synthesize magnetic Fe3O4 nanoparticles and to modify the surface of particles are presented in the present investigation. Fe3O4 magnetic nanoparticles were prepared by the co-precipitation of Fe3+ and Fe2+, NH3·H2O was used as the precipitating agent to adjust the pH value, and the aging of Fe3O4 magnetic nanoparticles was accelerated by microwave (MW) irradiation. The obtained Fe3O4 magnetic nanoparticles were characterized by Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), X-ray powder diffraction (XRD) and vibrating sample magnetometer (VSM). The average size of Fe3O4 crystallites was found to be around 8–9 nm. Thereafter, the surface of Fe3O4 magnetic nanoparticles was modified by stearic acid. The resultant sample was characterized by FT-IR, scanning electron microscopy (SEM), XRD, lipophilic degree (LD) and sedimentation test. The FT-IR results indicated that a covalent bond was formed by chemical reaction between the hydroxyl groups on the surface of Fe3O4 nanoparticles and carboxyl groups of stearic acid, which changed the polarity of Fe3O4 nanoparticles. The dispersion of Fe3O4 in organic solvent was greatly improved. Effects of reaction time, reaction temperature and concentration of stearic acid on particle surface modification were investigated. In addition, Fe3O4/polystyrene (PS) nanocomposite was synthesized by adding surface modified Fe3O4 magnetic nanoparticles into styrene monomer, followed by the radical polymerization. The obtained nanocomposite was tested by thermogravimetry (TG), differential scanning calorimetry (DSC) and XRD. Results revealed that the thermal stability of PS was not significantly changed after adding Fe3O4 nanoparticles. The Fe3O4 magnetic fluid was characterized using UV–vis spectrophotometer, Gouy magnetic balance and laser particle-size analyzer. The testing results showed that the magnetic fluid had excellent stability, and had susceptibility of 4.46×10−8 and saturated magnetization of 6.56 emu/g. In addition, the mean size d (0.99) of magnetic Fe3O4 nanoparticles in the fluid was 36.19 nm. 相似文献
69.
X. Yang 《Applied Surface Science》2006,252(10):3647-3657
The room-temperature adsorption and thermally induced processes of propionic acid and pyruvic acid on Ni(1 0 0) have been investigated by electron energy loss spectroscopy (EELS). Computational vibrational analysis of the optimized bidentate structures for acid-Ni model complexes (involving the organic acid and a Ni atom) has been performed by using the two-layer ONIOM method with the Density Functional Theory and used to interpret the vibrational EELS data. Dehydrogenation of the hydroxyl group is found to result in bonding of the carboxylate group in the propionate and pyruvate adspecies to either a single Ni surface atom in a bidentate configuration or two neighbouring Ni atoms in a bridge configuration. Given the similarities in the total energies and related vibrational frequencies obtained by the calculations in the case of pyruvate adspecies, it is difficult to differentiate the alternate adsorption structure, in which the keto O and hydroxyl O atoms are bonded to a Ni atom in a five-member chelate ring configuration. Furthermore, temperature-dependent EELS studies show that both the propionate and pyruvate adspecies could decompose upon annealing to above 400 K and further dissociate to CO adspecies above 550 K and to C and/or O above 600 K. 相似文献
70.
比浊法测定酸性镀铜液中微量氯离子 总被引:1,自引:0,他引:1
以乙二醇为增溶剂,硝酸银作沉淀剂,采用氯化银比浊法,在不分离硫酸铜的条件下,直接测定酸性镀铜液中微量氯离子。测定波长为440 nm,线形范围为0~50μg/25 mL,其表观摩尔吸光系数ε=1.3×105,方法检出限为0.035μg/mL,该法用于测定酸性镀铜液中微量氯离子在不同水平的加标回收率为95.4%~104.5%。结果表明,该法准确,快速,简便,其它的常见离子无干扰。 相似文献