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51.
A new model was proposed to predict the adsorption equilibrium of mixtures composed of supercritical gases. The adsorbed phase was visualized as a two-dimensional nonideal compressed gas. Pore size distribution was used to describe the energetic heterogeneity of the surface, and the two-dimensional virial equation was used as the local adsorption isotherm. The new model obtained is thermodynamically rigorous because it reduces to Henry's law as pressure approaches zero. The prediction performance of the new model was verified and compared with other models using the experimental data of a ternary mixture of CH4/N2/H2 and two binary mixtures of CH4/C2H4 and CH4/N2. Better performance was shown for all systems tested. 相似文献
52.
Mui C Senosiain JP Musgrave CB 《Langmuir : the ACS journal of surfaces and colloids》2004,20(18):7604-7609
We use density functional theory to investigate the surface chemistry of initial oxidation and hydroxylation of the Ge(100)-2 x 1 surface by water and hydrogen peroxide. Comparison of the reaction of water on the Si(100)-2 x 1 and Ge(100)-2 x 1 surfaces shows that the kinetics of oxidation of the Ge(100)-2 x 1 surface with water is slower. Our calculations also show that oxidation products on the Ge(100)-2 x 1 surface are less thermodynamically stable than on Si. We also investigate two competing dissociation reactions of H2O2 on the Ge(100)-2 x 1 surface. We find that dissociative adsorption via cleavage of the OH bond is less exothermic than OO dissociation. Furthermore, interdimer OO dissociation has a lower activation barrier than interdimer or intradimer OH dissociation, although interdimer dissociation products are found to be less stable compared than those formed from intradimer dissociation reactions. Finally, we find that the oxidation products formed from hydrogen peroxide are more stable than those formed from water. 相似文献
53.
Ochratoxin A (OTA) is a secondary fungal metabolite produced by several moulds, mainly by Aspergillus ochraceus, A. carbonarius, A. niger and by Penicillium verrucosum. The present work shows the results of comparative studies using different procedures for the analysis of OTA in maize bread samples. The studied analytical methods involved extraction with different volumes of PBS/methanol, different extraction apparatus, and clean-up through immunoaffinity columns. The separation and identification were carried out by high-performance liquid chromatography with fluorescence detection. The optimized method for analysis of OTA in maize bread involved extraction with PBS:methanol (50:50), and clean-up with IAC column. The limit of quantification was 0.033 ng g−1. Recoveries ranged from 87% to 102% for fortifications at 2.000 and 0.500 ng g−1, respectively, within-day R.S.D. of 1.4% and 4.7%. The proposed method was applied to 15 samples and the presence of OTA was found in nine samples at concentrations ranging from nd to 2.650 ng g−1. 相似文献
54.
Juan M. Kok Kevin C. Lim Brian W. Skelton Allan H. White 《Journal of Cluster Science》2004,15(3):377-386
The structural characterizations of some copper(I) halide (CuX) adducts with norbornadiene (nbd) are recorded. CuCl : nbd (1:1)4 (a redetermination), (2:1)2(|), are systems both based around Cu4Cl4 cubane-type cluster arrays. CuBr : nbd (7:3)(|)( 0.5 MeOH), a complex polymer with 3-symmetry, is believed to be the complex previously described as an adduct of 2:1 stoichiometry. Attempts to obtain an iodide counterpart have resulted in the definition of an ephemeral adduct CuI : MeCN (3:2)(|). 0.5 C7H8 in which, remarkably, the nbd is uncoordinated; the complex is a polymer, related to the [AgX(quinoline)](|) (X = Cl, Br) saddle polymer. 相似文献
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Propargylic alcohols are versatile precursors to many organic molecules including natural products and pharmaceutical compounds.[1] In our continuing interest in the development of practical methods for synthesis of ferrocene derivatives, we decided to investigate the efficiencies of ferrocenylacetylene addition to aromatic aldehydes under t-BuOKcatalyzed condition.[2] Interestingly, we found that the usually reliable coupling reaction between terminal alkyne of type 1 and aromatic aldehydes of type 2 does not furnish the expected propargylic alcohols, but that the isomeric aryl enones 3are found in high yield and very short reaction time (10~20 min). This provided a promising protocol for preparation of ferrocenyl chalcones in a practical, economical and mild sense compared with the traditional method. To the best of our knowledge, this unusual reaction was first observed for the addition of ferrocenylacetylene to aldehyde in a base-catalyzed manner (Eq. 1). 相似文献
59.
The Staudinger reaction of fluoroalkylazides were studied. A series of N-fluoroalkylimines were synthesized via aza-Wittig reaction of N-fluoroalkyliminophosphoranes. The N,N′-difluoroalkylated carbodiimide was also synthesized via the reaction of N-fluoroalkyliminophosphoranes with carbon dioxide or carbon disulfide. 相似文献
60.