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71.
Phenylacetylene hydrogenation on Pd, Pt and Pd–Pt/Al2O3 catalysts has been studied. In all catalysts activity was found not to depend on particle size. However, selectivity to styrene was found to depend on Pd/Al2O3 catalysts. Carbon deposition in both metal and support explains such a behavior. Nevertheless, in small Pd particles a longer residence time of styrene may control the selectivity. 相似文献
72.
An intelligent, automatic system based on an array of non-specific-response chemical sensors was developed. As a great amount of information is required for its correct modelling, we propose a system generating it itself. The sequential injection analysis (SIA) technique was chosen as it enables the processes of training, calibration, validation and operation to be automated simply. Detection was carried out using an array of potentiometric sensors based on PVC membranes of different selectivity. The diluted standard solutions needed for system learning and response modelling are automatically prepared from more concentrated standards. The electrodes used were characterised with respect to one and two analytes, by means of high-dimensionality calibrations, and the response surface of each was represented; this characterisation enabled an interference study of great practical utility. The combined response was modelled by means of artificial neural networks (ANNs), and thus it was possible to obtain an automated electronic tongue based on SIA. In order to identify the ANN which provided the best model of the electrode responses, some of the network's parameters were optimised and its usefulness in determining NH4+, K+ and Na+ ions in synthetic samples was then tested. Finally, it was used to determine these ions in commercial fertilisers, the obtained results being compared with reference methods. 相似文献
73.
Prisco Prete Antonino Fiorentino Luigi Rizzo Antonio Proto Raffaele Cucciniello 《Current Opinion in Green and Sustainable Chemistry》2021
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74.
75.
We study the Boltzmann-Grad limit in various versions of the two-dimensional HPP cellular automaton. In the completely deterministic case we prove convergence to an evolution that is not of kinetic type, a well-known phenomenon after Uchyiama's paper on the Broadwell gas, whereas the limiting equation becomes of kinetic type in the model with random collisions. The main part of the paper concerns the case where the collisions are deterministic and the randomness comes from inserting, between any two successive HPP updatings,
- stirring updatings, <1 being any fixed positive number and a parameter which tends to 0. The initial measure is a product measure with average occupation numbers of the order of (low-density limit) and varying on distances of the order of –1. The limit as 0 of the system evolved for times of the order of
-1- corresponds to the Boltzmann-Grad limit. We prove propagation of chaos and that the renormalized average occupation numbers (i.e., divided by) converge to the solution of the Broadwell equation. Convergence is proven at all times for which the solution of the Broadwell equation is bounded. 相似文献
76.
G. Del Piero M. Cesari S. Cucinella A. Mazzei 《Journal of organometallic chemistry》1977,137(3):265-274
The compounds [((THF)Mg)(HA1N-t-Bu)3] (I) and [((THF)3Ca)(HA1N-t-Bu)3] · THF (II) have been structurally characterized from single-crystal diffraction data. The molecular structures are based on an (A1N)4 “cubane” type framework in which an aluminum is replaced by an alkaline earth metal. According to the size and the coordination of the “foreign” atom (four for Mg, six for Ca) the cubic geometry of the cage is increasingly distorted. Coordination is completed by one molecule of THF to the Mg atom and three molecules to the Ca atom; in II a molecule of THF crystallizes with a cage molecule. Mean MgN and CaN bond distances are 2.090(4) and 2.490(2) Å. Crystal data: I, orthorombic, space group Pbca, a 17.107(2), b 17.305(4) and c 20.220(5) Å, Z = 8, calculated density 1.031 g/cm3; II, orthorombic, space group Pbca, a 20.48(1), b 20.38(1), c 20.51(1), Z = 8, calculated density 1.081 g/cm3. 相似文献
77.
Raffaele Battistuzzi 《Transition Metal Chemistry》1988,13(6):401-409
Summary 1-Phenyl-4,6-dimethylpyrimidine-2-thione (L) and its protonated cation 1-phenyl-4,6-dimethyl pyrimidinium-2-thione
, have been employed to prepare the following copper(I) complexes: CuXL (X=Cl, Br, I, ClO4 or BF4), (CuX)3L2 (X=Cl, Br, I or SCN), (CuX)2L5 (X= ClO4 or BF4) and the zwitterionic species CuXY(LH) X=Y=Cl, Br or I; X=Br; Y=Cl; X=I; Y=Br). Chemical analysis, conductivity, and near-and far-i.r. spectroscopic data are presented and the chemical relationships between them discussed in terms of postulated dinuclear or polynuclear species for the complexes. Metalligand vibrations suggest that the neutral ligand is N, S-bidentate in its copper(I) complexes as well as S-coordinat for the
cation in the zwitterionic compounds. Diagnostic i.r. bands frequencies of counterions and (Cu–X) modes indicate the coordinating character of Cl–, Br–, I–, SCN– and of ClO
4
–
, BF
4
–
(in CuXL) anions. For the chloro-complexes CuClL and (CuCl)3L2, salt-like species of the [CuL2][CuCl2] and [{Cu2L2Cl}n] [CuCl2]n type respectively, are proposed. The polarographic data for the perchlorate complexes have shown that in dimethylformamide (DMF) solution, the prevailing species are CuClO4L, CuClO4L2 and (CuClO4)2L5; their overall stability constants were determined. 相似文献
78.
E. Delée L. Le Garrec I. Jullien S. Béranger J. C. Pascal H. Pinhas 《Chromatographia》1987,24(1):357-359
Summary A routine chiral analysis has been developed to control the optical purity of chiral drugs and to monitor their asymmetric
synthesis. The recent advent of new chiral stationary phases for HPLC enabled us to achieve the direct resolution of chiral
drugs without any derivatization.
The factors affecting chiral resolution on a new alpha1-acid glycoprotein column (EnantioPac, LKB) were assessed with three beta-aminoalcohols. 相似文献
79.
This paper deals with the synthesis of six σ-cyclohexylethynyl complexes of CoII and FeII and their characterization by chemical analysis, infrared and 1H NMR spectra, and magnetic measurements. Four of them are six-coordinate complexes, unsubstituted or substituted, namely K4[M(C≡C—C6H11)6] nNH3(M = Co, n = 2; M = Fe, n = 0), K2[Co(C≡C6H11)4(NH3)2] and K4[Fe(CN)4-(C≡C—C6H11)2]. Two are four-coordinate complexes of formula [(Ph3P)2M-(C≡C6H11)2] (M = Co, Fe). All are low-spin complexes, the magnetic moment for the six-coordinate Co(II) complexes, measured at various temperatures, being intermediate between low- and high-spin values. 相似文献
80.
Michelini Mdel C Russo N Alikhani ME Silvi B 《Journal of computational chemistry》2005,26(12):1284-1293
The interaction between molybdenum, atom, and dimer, with nitrous oxide has been investigated using density functional theory. The analysis of the potential energy surfaces for both reactions has revealed that a single molybdenum atom can activate the N--O bond of N2O requiring a small activation energy. However, the presence of several intersystem crossings between three different spin states, namely, septet, quintet and triplet states, seems to be the major constraint to the Mo + N2O reaction. Contrarily, the low-lying excited states (triplet and quintet) do not participate in the reaction between the molybdenum dimer and N2O. The latter reaction fully evolves on the singlet spin surface. Three different regions have been distinguished along the pathway: formation of an adduct complex, formation of an inserted compound, and the N2 detachment. The connection between the two first regions has been characterized by the formation of a special complex in which the N--O bond is so weakened that it could be considered as a first step in the insertion process. It has been shown that the topological changes along the pathways provide a clear explanation for the geometrical changes that occur along the reaction pathway. In summary, the detachment of the N2 molecule is found to be kinetically an effective process for both reactions, owing to the high exothermicity and consequently to the high internal energy of the insertion intermediates. However, in the case of Mo atom, the reaction should be a slow process due to the presence of spin-forbidden transitions. These results fully agree with previous experimental works. 相似文献