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51.
The intermolecular vibrational energy transfer from triplet molecules of benzophenone and anthraquinone to H2O molecules has been investigated. To determine the rates of establishment of vibrational (V-V) and thermal (V-T) equilibrium in a vibrational quasi-continuum of mixed singlet-triplet levels, the dependences of the decay rates and intensities of the fast and slow components of delayed fluorescence on the H2O vapor pressure have been investigated. For V-V relaxation, the efficiencies 1 and the mean energies E transferred per collision in mixtures with H2O and other polyatomic foreign gases have been compared. It has been established that the efficiencies 1 for quasi-resonant vibrational energy transfer (V-V) from benzophenone and anthraquinone to H2O are an order of magnitude lower than the gas-kinetic ones and lower than those obtained under the same experimental conditions for such foreign gases as C5H12, SF6, and CCl4, and decrease with increasing temperature in the 433–513 K range. It has been concluded that the mechanism of V-V relaxation in mixtures with H2O are determined by long-range attractive forces. In mixtures with H2O, no acceleration of V-T relaxation due to the formation of hydrogen bonds has been revealed. The low-efficiency thermalization process (V-T relaxation) is controlled by short-range repulsive forces, and the differences between the intensities 2 for mixtures of benzophenone and anthraquinone with H2O and other polyatomic gases are determined by the change in the reduced mass of interacting molecules. 相似文献
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53.
针对井下甲烷浓度监控干扰大的问题,结合实时监测甲烷浓度的系统要求,设计角镜连动的自消震光学结构,构建了基于无线网络的实时数据通信系统.在干涉系统中,固定两个角镜位置,将两片半透半反镜用连杆结构同步旋转,由此产生光程差.由于采用了连杆结构,任意时刻引入的震动在两个分束镜上等量存在,其结果是差分值,可实现完全相消.由分析分束器的最大旋转范围计算得到系统的光程差变化范围.结合比尔朗伯定律,给出系统在井下工作的甲烷气体浓度最低检出限.分别在实验室及矿井主巷道中完成实验过程,通过化学反应法求得被测甲烷气体的标准浓度,与WQF530型光谱分析仪的测试结果作比较,结果表明:在实验室无干扰条件下,两种检测方法的相对误差均小于1.0%;在井下实验中,传统光学检测方法受环境影响明显,相对误差大幅增加,而本系统测试结果基本稳定,具有较强的抗干扰能力及较高的稳定性. 相似文献
54.
A.J. Groszek 《Applied Surface Science》2007,253(13):5882-5887
Exposure of pure iron nano-flakes to hydrogen generates a high heat evolution associated with hydrogen uptakes shown by flow-through microcalorimetry. A large part of the hydrogen was found to be irreversibly absorbed by the iron flakes at 220 °C and atmospheric pressure, but an increased desorption of hydrogen was achieved by noble gases, such as helium and argon. Thus the iron surfaces displayed strong affinity for hydrogen, but also, surprisingly, for the noble gases, which were found to be able to displace hydrogen from the iron surfaces.The uptake of hydrogen by the iron flakes was observed to reach 9 wt.% after exposure for 5 h, which may be of interest in hydrogen storage applications. Desorption with the help of argon may provide an acceptable method of hydrogen recovery. 相似文献
55.
Luciano A. Leal Wiliam F. da Cunha Luiz F. Roncaratti Geraldo M. e Silva 《Molecular physics》2016,114(3-4):440-445
ABSTRACTBased on ab initio calculations, our research group has built an analytical ground-state potential energy surface (PES) for hydrogen peroxide– noble gas (Ng) interactions, such as H2O2–He, H2O2–Ne, H2O2–Ar, H2O2–Kr, and H2O2–Xe complexes. From this PES, it was verified that the Ng presence does not affect the equilibrium values of the H2O2 dihedral angles. This happens because the H2O2 intramolecular barriers have much higher energies than the atom–bond interaction within these complexes. From this point of view, it is indeed reasonable to consider the H2O2 system as a rigid rotor, frozen at its equilibrium configuration. We present in this work the torsional motion for the H2O2 isolated system, the vibration–rotation energy levels and spectroscopic constants for hydrogen peroxide–noble gas by using the aforementioned PES. The predicted H2O2 torsional motions are in good agreement with both theoretical and experimental results available in the literature. Regarding H2O2–Ng ro-vibrational energies and spectroscopic constants, it is the first time that these calculations are presented in the literature. The current theoretical predictions are expected to be useful in the future experimental investigations. 相似文献
56.
In our previous work (Hu et al., 2014), a method has been proposed to detect gas compositions by locating the acoustic spectral peaks, which can be detected only by two-frequency acoustic measurements in practice. However, as a ‘Detection Calibration’, the effective relaxation area (ERA) constructed by existing theoretical model cannot match the two-frequency measurements when there are more than one strong relaxational components in gas mixtures. This paper proposes a method to construct the ERA by coupling the decoupled single relaxation times together to a whole relaxation time. For gas mixtures with only one single relaxation process, the predicted ERA results match with the experimental data better than those predicted by the existing model. Moreover, for gas mixtures in which more than one relaxation process are significant, the ERA results predicted by the proposed method also match with the detection results of two-frequency measurements better than the existing model. This relaxation time coupling based ERA constructing method is validated by the application in low-quality natural gas detection. 相似文献
57.
58.
ABSTRACT We analyze the influence of random errors and absorption shape fitting errors on gas concentration measurement in tunable diode laser absorption spectroscopy. We then propose a new data processing method according to the characteristic of random errors and fitting absorption shape. This method only uses the integral value within the half width at half maximum of the fitting absorption shape to determine the gas concentration in actual measurements. Meanwhile, the O2 transition at 13,150.197 cm?1 is selected to measure the O2 concentration using this method. Compared with the traditional method, the method established in this paper can accurately measure O2 concentration. 相似文献
59.
Abstract This review article describes some existing microplasma sources and their applications in analytical chemistry. These microplasmas mainly include direct current glow discharge (DC), microhollow-cathode discharge (MHCD) or microstructure electrode (MSE), dielectric barrier discharge (DBD), capacitively coupled microplasmas (CCμPs), miniature inductively coupled plasmas (mICPs), and microwave-induced plasmas (MIPs). The historical development and recent advances in these microplasma techniques are presented. Fundamental properties of the microplasmas, the unique features of the reduced size and volume, as well as the advantageous device structures for chemical analysis are discussed in detail, with the emphasis toward detection of gaseous samples. The analytical figures of merit obtained using these microplasmas as molecular/elemental-selective detectors for emission spectrometry and as ionization sources for mass spectrometry are also given in this review article. 相似文献