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31.
The photophysics and photochemistry of alpha-terthiophene (alphaT), compartmentalized in mixed nonionic/anionic micelles, have been investigated with focus on the influence of the micellar surface charge density on the formation of the radical coupling product alpha-hexathiophene (alphaH). By varying the ratio of nonionic-to-anionic surfactants, and assuming ideal mixing, the charge density of the mixed micelles was varied. From Poisson-Boltzmann calculations, performed using the cell model, the electrostatic potential and the counterion activity were estimated as a function of the distance from the micellar surface. Upon excitation, the triplet state of alphaT is formed, from which the alphaT radical cation can be formed by absorption of a second photon. The radical cation can form alphaH if it encounters another alphaT radical cation. Under the experimental conditions used, this implies that the alphaH formation only occurs if the compartmentalized radical cation is able to migrate from its host micelle to another micelle, either via the surrounding bulk or by fusion of two micelles followed by mixing of their contents before micellar fission. The formation yield of the radical cation depends on the charge density of the mixed micelle; a lower charge density, that is, an increased amount of nonionic surfactant, lowers the yield. The yield of the coupling product alphaH, however, does not follow the same trend. A maximum yield of alphaH is found at intermediate nonionic surfactant molar ratios. This behavior is understood in terms of the Poisson-Boltzmann simulation results and by comparing charge-density changes as a function of molar fraction with the changes in counterion activity. The alphaH yield is a result of the balance between an increased possibility of radical cation bulk migration and a lowered electrostatic stabilization of the radical. 相似文献
32.
Cabaleiro-Lago EM Rodríguez-Otero J García-López RM Peña-Gallego A Hermida-Ramón JM 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(20):5966-5974
A comprehensive B3LYP/6-31+G* study on the electrocyclization of 1,2,4,6-heptatetraene analogues was conducted. Starting from the cyclization of (2Z)-2,4,5-hexatrienal, a pericyclic disrotatory process favored by the assistance of a electron lone pair, we incorporated small modifications in its molecular structure to obtain a truly pseudopericyclic process. To this purpose electronegative atoms (fluorine and nitrogen) were added to give a more electrophilic character on the carbon atom which is attacked by the electron lone pair of the oxygen atom. The complete pathway for each reaction was determined, and changes in magnetic properties were monitored with a view to estimating the aromatization associated with each process. This information, together with the energetic and structural results, allowed us to classify the reactions as pseudopericyclic or pericyclic. Among all studied reactions only one was a truly pseudopericyclic process and another was a borderline case. The features of this unequivocally pseudopericyclic case were analyzed in depth. 相似文献
33.
Ângela F. S. S. Mendonça Dina T. R. Formigo Isabel M. S. Lampreia 《Journal of solution chemistry》2002,31(8):653-670
Solubilities of triethylamine in aqueous tetraethylammonium chloride solutions were measured at 20, 25, and 35°C. The molalities in Et4NCl of the aqueous solvents ranged from 0.03 to 1 mol-kg–1. The data were evaluated from density measurements using a vibrating-tube densimeter. At each temperature, least-squares method was used to fit experimental density data points to double polynomial equations of various degrees. Triethylamine molalities of the saturated aqueous phases were estimated by extrapolation from those equations. Experimental data were interpreted in terms of hydrophobic and electrostatic perturbed domains in the hydration shells of the noneleceory and of the cation of the salt, as a function of temperature and salt concentration. The conclusions obtained are consistent with previous volumetric studies. 相似文献
34.
The adsorption equilibrium of water on microporous adsorbents (zeolites of NaA-, NaY- and NaX-type as well as their ion exchanged
forms) and on mesoporous adsorbents (different silica gels and composite material i.e. silica gel + salt hydrate) has been
studied experimentally and theoretically. Using the Dubinin theory of pore filling the characteristic curves of the adsorption
systems and other relevant dependences such as isotherms, isobars, isosteres and the curve of the differential heat of adsorption
were calculated. For all systems investigated the adsorption were calculated. Aads and the desorption potential Ades of the closed heat storage system were estimated. These values define the working range of the adsorption/desorption cycle
and allow to calculate the specific heat storage density Δ hsp. On the basis of Δ hsp the different adsorbents were compared in order to select the optimal porous storage material for a given application.
The presented experimental and theoretical investigations show that the adsorption systems water-zeolite and water-composites
are promising working pairs for thermochemical heat storage processes for hot tap water supply and space heating of single
family dwellings. The advantage of the water-composite system is the low desorption temperature (solar energy) the main shortcoming
the low temperature lift. The advantage of the water zeolite system is the high temperature lift, the shortcoming are the
relative high desorption temperatures. 相似文献
35.
The partial molal volumes of Li+, Na+, K+, Rb+, Cs+, Cl–, Br–, I–, and NO
3
-
in DMSO at 25°C have been determined from ultrasonic vibration potential data and density data for solutions of uni-univalent electrolytes. Hepler's semiemprirical equation has been used to split ionic partial molal volumes into geometric and electrostrictive contributions. The results obtained in this work confirm the conclusion of our previous studies, namely, that the contribution of electrostriction is essentially determined by the properties of that layer of atoms, 0.3 to 0.4 nm thick, in contact with the ion and by the degree of steric hindrance of the poles of the dipole of the solvent molecule. On the other hand, the geometric contribution depends on the size of the solvent molecule and also on the arrangement of the solvent molecules about the ions. It is shown that the geometric contribution to the partial molal volume of ions is largely increased when ions cannot come close enough to the poles of the solvent-molecule dipole, owing to steric hindrance. 相似文献
36.
The regions of variation of density, enthalpy of formation, and detonation velocity of all of the formally possible structual isomers were determined for several molecular formulas of C,H,N,O-containing explosives. The histograms of the distribution of the structual isomers over these parameters were constructed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 859–862, May, 1995.The authors are grateful to Mrs. I. D. Solodukhina for the design of the graphical material.The work was carried out with the financial support of the Russian Foundation for Basic Research (Project No. 94-03-09323). 相似文献
37.
ZnO压敏电阻器生产工艺的改进 总被引:4,自引:0,他引:4
压敏电阻器的生产工艺是影响产品质量的重要因素之一。通过试验,对生产工艺中,影响ZnO压敏电阻器直流老化性能的因素,如原材料细度、烧成气氛、成型密度、热处理温度和时间、掺杂等进行了研究,并据此确定了最佳工艺条件。 相似文献
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为了探测敌方激光的来袭方向,开发了一种激光脉冲方向告警系统.该系统由光学模块、信号处理模块和显示模块组成,其探测范围为水平方向0°~360°,垂直方向0°~90°,角度分辨率30°,识别出波长为0.85,1.06和1.54 μm,脉宽不小于10ns的激光脉冲,探测功率密度下限为1 mW/cm2,其探测概率达到98%以上... 相似文献