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41.
42.
The study is concerned with analysis of the energies of formation (E), frequency shifts (Δν) in IR spectra, ionization potentials (IP) of H-complexes, hydrogen bond lengths (r), and spin densities (sd) in H-complexes involving radical cations, obtained from quantum chemical calculations for 20 series
of H-complexes. It was for the first time established that the E, IP, r, and sd values and the changes in enthalpy (δH) depend not only on the inductive and resonance effects but also on the polarizability effect of the substituents bound to
the donor and acceptor centers in the H-complexes. Interrelations between the polarizability effect and the molecular structure
of H-complexes are considered.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 602–608, April, 2006. 相似文献
43.
44.
诱导效应指数与含硫含氮的低碳直链有机化合物的标准汽化热 总被引:2,自引:0,他引:2
本文利用诱导效应指数建立了含硫含氮的低碳直链有机物的标准汽化热的简单估算方法,我们利用此法计算了一些含硫含氮的直链有机物的标准汽化热,41个可比较值的相对误差均在5%以内。 相似文献
45.
Fu-Ken Liu 《Analytica chimica acta》2005,528(2):249-254
This paper demonstrates that capillary electrophoresis (CE) can be employed for characterizing the sizes of nanometer-scale gold particles. We characterized the gold nanoparticles by effecting CE separation using a buffer of SDS (70 mM) and 3-cyclohexylamino-1-propanesulfonic acid (CAPS; 10 mM) at pH 11.0 and an applied voltage of 18 kV and obtained a linear relationship (R2 > 0.99) between electrophoretic mobilities and size for nanoparticles whose diameters fall in the regime from 5.0 ± 0.5 to 41.2 ± 3.3 nm; the relative standard deviations of these electrophoretic mobilities are <0.8%. We evaluated the feasibility of employing these separation conditions for the size characterization by of gold nanoparticle samples that were synthesized by a rapid microwave heating method. We confirmed that this CE method is a valid one for size characterization by comparing the results obtained by CE with those provided by scanning electron microscopy (SEM); a good correlation exists between these two techniques. Our results demonstrate that CE can be employed to accelerate the analysis of the sizes of nanomaterials. 相似文献
46.
Ion mobility spectrometry (IMS) is a proven technology for detection of vapor phase chemical warfare agents. The technology is suitable for field portable instrumentation due to its small size, high sensitivity, speed of analysis, and low power consumption. However, it suffers from a limited dynamic range and potential difficulties in identifying compounds in complex matrices. The use of gas chromatography (GC) coupled to IMS can overcome the difficulty of chemical identification in mixtures by separating the sample into individual components before detection. Using this approach, IMS technology has previously been adapted to detect biological aerosols using an open tube pyrolyzer and a short GC column (Py-GC-IMS). The open sample introduction tube of a Py-GC-IMS instrument would be a convenient configuration to accept aerosol particulates, and while viewed as needed for aerosol trapping, is not optimal for liquid chemical analyses. To examine the usefulness of an existing Py-GC-IMS system for analysis of chemicals in water, an existing open-port sample interface was replaced with a septum-equipped closed tube injector to contain analyte vapors resulting from liquid injection. Tributylphosphate (TBP) was used as a surrogate chemical warfare agent, and aqueous injections into both closed and open tube assemblies were performed. Sample introduction into the closed tube inlet was also accomplished using solid phase microextraction (SPME) preconcentration. The limit of detection for TBP using an open tube, closed tube, and closed tube configuration with SPME sample introduction was 0.980, 0.196, and 0.0098 mg/L, respectively. 相似文献
47.
微波增压溶样-石墨炉原子吸收光谱法同时测定植物性样品中微量铅镉 总被引:7,自引:2,他引:7
使用微波增压溶样法,将样品用HNO3—HClO4溶解后,用石墨炉原子吸收光谱法同时测定植物性样品中铅和镉。以磷酸二氢铵—硝酸镁作为基体改进剂,可使灰化温度大大提高,克服了基体的干扰。铅和镉的回收率分别为95.3%—104.8%和96.2%—105.5%,RSD分别为4.8%-7.2%和4.3%-7.6%。 相似文献
48.
Influence
of heating rate on kinetic quantities of solid phase thermal decomposition 总被引:1,自引:0,他引:1
Thermogravimetric
analyses of thermal decomposition (pyrolysis, thermal dissociation and combustion)
of 9 different samples were carried out in dynamic conditions at different
heating rates. The kinetic parameters (E, A and km)
of thermal decomposition were determined and interrelations between the parameters
and heating rate q were analyzed. There
were also relations between Arrhenius and Eyring equations analyzed for thermal
decomposition of solid phase. It was concluded that Eyring theory is an element,
which interconnects used thermokinetic equations containing Arrhenius law
and suggests considering kinetic quantities in way relative to 3 kinetic constants
(E, A
and km). Analysis
of quantities other than km (i.e. E, A, Δ+H, Δ+S) in relation to heating rate is an incomplete method
and does not lead to unambiguous conclusions. It was ascertained that in ideal
case, assuming constant values of kinetic parameters (E
and A) towards heating rate and satisfying
both Kissinger equations, reaction rate constant km
should take on values intermediate between constants (km)1
and (km)2
determined from these equations. Whereas behavior of parameters E and A towards q were not subjected to any rule, then plotting relation km vs. q in the background of (km)1
and (km)2
made possible classification of differences between thermal decomposition
processes taking place in oxidizing and oxygen-free atmosphere. 相似文献
49.
It has been shown that functionalised pyrroles can be efficiently prepared using a two-step sequence. This sequence involves the propargylation of secondary enaminones using n-BuLi and propargyl bromide, followed by intramolecular hydroamination catalysed by silver nitrate. The hydroamination can be carried out at room temperature (overnight) or in a domestic microwave oven (60 s). 相似文献
50.
锂离子电池正极材料LiMn2O4的低热固相合成与性能表征 总被引:6,自引:0,他引:6
锂离子电池具有比能量高、环境污染小等优点,广泛应用于手提电话、便携式电脑、摄像机等设备中。其正极材料的研究是锂离子电池的研究重点。层状结构的LiCoO2、LiNiO2和尖晶石结构的LiMn2O4是仅有的三种能在3.5V以上电位可嵌入Li的正极材料[1~3]。目前市售的锂离子电池主要采用LiCoO2作正极材料,但由于Co资源缺乏和价格相对昂贵,而锰资源丰富,价格低廉且无毒,对环境友好,因此世界各国都在大力进行以LiMn2O4为正极材料的锂离子电池的实用化研究。LiMn2O4传统的制备方法是高温固相反应合成法[4~7],但由于Mn的变价多,与Li形成贫Li或… 相似文献