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31.
Mohamed El Guendouzi Abderrahim Dinane Abdelfetah Mounir 《Journal of solution chemistry》2002,31(2):119-129
The mixed aqueous electrolyte system of ammonium and lithium chlorides has been studied by the hygrometric method at 25°C. The relative humidities of this system are measured at total molalities from 0.3 to 6 mol-kg– 1 for different ionic-strength fractions y of NH4Cl with y = 0.33, 0.50, and 0.67. The data obtained allow the deduction of new water activities and osmotic coefficients. The experimental results are compared with the predictions of the ECA (extended composed additivity) law proposed in our previous work. The Zdanovskii–Stokes–Robinson (ZSR), the Robinson–Stokes (RS), Reilly–Wood–Robinson (RWR), the Pitzer, and the Lietzke–Stoughton (LS II) models are also compared with our results. Predictions made using these models are, in general, consistent with our results. From these measurements, new Pitzer mixing ionic parameters are determined and used to predict the solute activity coefficients in the mixture for different ionic-strength fractions. 相似文献
32.
The reaction paths for the transformations of substituted acetylenes (X—CC—Y; X, Y = H, Me, Ph, CN) in reaction with phenylsulfenium cation were studied by quantum-chemical methods. It was shown that the reactions take place with the formation of acyclic and cyclic cationic intermediates. The factor that determines the structure and characteristics of these cations is the induction and polarizing action of the substituents in the acetylenes and to a lesser degree their electron-donor characteristics. The resonance effect of the phenyl substituent has a predominantly levelling action on the distribution of charges. 相似文献
33.
5,6-Bis(dimethylamino)acenaphthylene is readily involved in [4+2] cycloaddition reactions with symm-tetrazine derivatives to form new proton sponges with the diazafluoranthene skeleton. Under analogous condition, 1,8-bis(dimethylamino)-4-vinylnaphthalene gave 4-pyridazinyl derivatives. The relative reactivities of 5,6-bis(dimethylamino)acenaphthylene, 1,8-bis(dimethylamino)-4-vinylnaphthalene, 5-dimethylaminoacenaphthylene, and acenaphthylene in the reactions with 3,6-diphenyl-symm-tetrazine are in a ratio of 32 : 17 : 14 : 1. The site of protonation of 3,4-bis(dimethylamino)-7,10-diphenyl-8,9-diazafluoranthene is controlled by the basicity of the solvent. The reaction in acetonitrile afforded the cation stabilized by an intramolecular hydrogen bond, whereas the reaction in dimethyl sulfoxide gave rise to the resonance-stabilized cation. 6,7-Bis(dimethylamino)phenalen-1-one was protonated only at the carbonyl group. 相似文献
34.
Guerrero-Alvarez JA Moncayo-Bautista A Ariza-Castolo A 《Magnetic resonance in chemistry : MRC》2004,42(6):524-533
The relative configuration of 11 1,4-diazaspiro[4.5]decanes (1a-1j and 1m), 15 1,4-oxazaspiro[4.5]decanes (2a-2o) and 10 1,4-dioxaspiro[4.5]decanes (3a-3n) substituted at the 2-, 6-, 7- or 8-position by a methyl group or using the tert-butyl group as a model for the ananchomeric structure is reported. The relative stereochemistry was analyzed by 1H, 13C, 15N and 17O NMR and all isomers present were characterized spectroscopically. Compounds with a methyl group in the six-membered ring show a chair conformation preference with the methyl group in the equatorial position. Compounds with one or two nitrogens exhibit a tautomeric equilibrium between the imine-diazolidine forms, as demonstrated by IR and 13C NMR. 相似文献
35.
分别用MNDO和AM1两种半经验方法,对C59F2nHN (n = 1, 2) 的异构体进行几何构型全优化,结合频率分析及HF/6-31G单点能计算,确定了各异构体的基态结构及其相对稳定性。计算结果表明,C59HN的F加成物的立体选择性规律与C60的不同,最稳定异构体不是1-2加成物。C59F2HN的最稳定异构体是1-4加成的6, 18-或12, 15-异构体; C59F4HN的最稳定异构体是1-4,1-4加成的6, 18; 12, 15-异构体,其能量远小于其它各异构体的能量。N原子取代碳笼骨架C原子后,改变了碳笼F加成物的立体选择性规律。 相似文献
36.
Andrea Posilicano 《Potential Analysis》1996,5(3):241-271
We prove a convergence theorem for sequences of Diffusion Processes corresponding to Dirichlet Forms of the kind
.We obtain convergence in total variation norm of the corresponding probability measures on the path space C(+;d) under hypotheses which, for example, are satisfied in the case of H
loc
1
(
d
)-convergence of the 's, but we can allow more singular situations as regards the approximating sequences. We use then these results to give a criterion of convergence for generalized Schrödinger operators in which the potential function should not necessarily exists as a measurable function. We obtain convergence not only in strong resolvent sense, but we also obtain convergence in the uniform operator topology up to sets of arbitrarily small Lebesgue measure. Applications to the problem of the approximation of ordinary Schrödinger operators by generalized ones corresponding to zero-range interactions are given. 相似文献
37.
Yi-Lu Sun Ren-Jang Wu Yu-Ching Huang Pi-Guey Su Murthy Chavali Yi-Zhen Chen Chu-Chieh Lin 《Talanta》2007,73(5):857-861
In situ preparation of polypyrrole (Ppy) by photo-polymerization coated on a quartz crystal microbalance (QCM) as a low humidity sensor was reported. Different concentrations of Ppy films say 0 wt.% (as blank), 0.1, 1, and 10 wt.% were investigated to measure humidity concentrations between 14.7 and 5412.5 ppmv. The adsorption/desorption behavior was also examined at humidity concentration 510.2 ppmv. The sensitivities of 0, 0.1 and 1 wt.% Ppy films at 51.5 ppmv were 0.143, 0.219 and 0.427, respectively. For 1 wt.% Ppy, the highest sensitivity was obtained. The slope and correlation coefficients (R2) for 1 wt.% Ppy at the ranges of 14.7–898.6 ppmv were 0.0646 and 0.9909, respectively. A series of molecular simulations have been carried out to calculate bond energy for the water molecule interaction with Ppy, which was found to be 3 kcal/mol indicating the existence of hydrogen bonding during the sorption process. Based on Langmuir isotherm adsorption assumption, for 0.1 and 1 wt.% Ppy films, the association constants were 2606.30 and 5792.98, respectively. This larger association constant for 1 wt.% Ppy film explains higher sensitivity. 相似文献
38.
In this paper,large-sized sapphire (230×210 mm,27.5 kg) was grown by SAPMAC method (sapphire growth technique with micro-pulling and shoulder-expanding at the cooled center). Dislocation peculiarity in large sapphire boule (0001) basal plane was investigated by chemical etching,scanning electron microscopy and X-ray topography method. The triangular dislocation etch pit measured is 7.6×101~8.0×102 cm-2,in which relative high-density dislocations were generated at both initial and final stages of crystal growth. The analysis of single-crystal X-ray topography shows that there are no apparent sub-grain boundaries; the dislocation lines are isolated and straight. Finally,the origins of low-density dislocation in sapphire crystal are discussed by numerical analysis method. 相似文献
39.
Inorganic-organic hybrids have been synthesized by incorporation of the inorganic component of Ti(OC2H5)4 into the organic polymer of ethyl cellulose. The inorganic-organic hybrids did not dissolve in toluene used as a solvent for the starting materials. The ethanol was formed as a by-product of the alcoholysis condensation reaction between Ti(OC2H5)4 and ethyl cellulose. These results suggest that ethoxy groups of Ti(OC2H5)4 react with hydroxy groups of ethyl cellulose to form cross-linking bonds of –O–Ti–O–. The reaction of Ti(OC2H5)4 with ethyl cellulose was further investigated by Fourier transform infrared (FT-IR) spectroscopy. The FT-IR spectroscopic experiments revealed that the Ti–O bond state of Ti(OC2H5)4 was changed by refluxing a toluene solution of Ti(OC2H5)4 with ethyl cellulose. The inorganic-organic hybrids have an interesting dielectric property; their dielectric constant is higher than that of ethyl cellulose and that of a simple mixture of TiO2 and ethyl cellulose. 相似文献
40.
A. B. Terent'ev S. I. Gapusenko T. T. Vasil'eva S. V. Vitt 《Russian Chemical Bulletin》1992,41(9):1567-1571
The relative rate constants of the addition of the C6H5CH2 radical to unsaturated compounds CH2=CHX (X = C4H9, SiMe3, CF3, CO2Me, CN) were determined under the conditions of initiation by the Fe(CO)5 + DMF system or by benzoyl peroxide. Depending on the values of the relative addition rate constants, the monomers can be arranged into the following series (X): CF3C4H932Me5 + DMF system, the addition stage proceeds by a free radical mechanism.A. N. Nesmeyanov Institute of Heteroorganic Compounds, Russian Academy of Sciences, 117813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 9, pp. 2017–2022, September, 1992. 相似文献