Theoretical and computational investigations of nucleation have been plagued by the sensitivity of the phase diagram to the range of the interaction potential. As the surface tension depends strongly on the range of interaction potential and as the classical nucleation theory (CNT) predicts the free energy barrier to be directly proportional to the cube of the surface tension, one expects a strong sensitivity of nucleation barrier to the range of the potential; however, CNT leaves many aspects unexplored. We find for gas-liquid nucleation in Lennard-Jones system that on increasing the range of interaction the kinetic spinodal (KS) (where the mechanism of nucleation changes from activated to barrierless) shifts deeper into the metastable region. Therefore the system remains metastable for larger value of supersaturation and this allows one to explore the high metastable region without encountering the KS. On increasing the range of interaction, both the critical cluster size and pre-critical minima in the free energy surface of kth largest cluster, at respective kinetic spinodals, shift towards smaller cluster size. In order to separate surface tension contribution to the increase in the barrier from other non-trivial factors, we introduce a new scaling form for surface tension and use it to capture both the temperature and the interaction range dependence of surface tension. Surprisingly, we find only a weak non-trivial contribution from other factors to the free energy barrier of nucleation. 相似文献
AbstractThe synthesis conditions of HZSM-5 zeolite, including crystallization temperature, crystallization time and raw material ratio, were investigated by L32 (48) orthogonal test to specifically optimize its performance in dimethyl ether (DME) aromatization for the first time. Based on the total yield of aromatic products, the synthesis conditions of HZSM-5 zeolite with the best DME aromatization properties were obtained by comprehensive analysis and validation experiments. The relationship between the aromatization performance, crystalline structure, pore structure, and acidity of HZSM-5 zeolite were analyzed. The results showed that the HZSM-5 zeolite accompanied by hierarchical structure, an appropriate Brønsted and Lewis acid content and uniform crystal morphology, was successfully synthesized under optimized conditions. Over this unmodified and un-doped catalyst, the conversion of DME approached to 99.3% and the total yield of aromatics reached was 53.5%. 相似文献
In this paper an alternative approach for measurement of στ product for 4F3/2→4I11/2 transition of Nd3+ doped YVO4 crystal is reported. In this method a microchip laser is formed by keeping a small piece of the sample in plane-plane resonator
and a diode laser (808 nm) is used for pumping. The pump power induced thermal lensing effect is used to make the cavity stable.
The cavity mode area is estimated by measuring the thermal lens focal length at the threshold and the average pump area is
measured by Gaussian fit to the intensity profiles of the pump beam. The value of στ product of Nd:YVO4 crystal obtained by this method is within 10% of the reported values. The advantage of this method is that it is a simple
method for direct measurement of στ product of laser crystals. 相似文献
Summary. Upon condensation with 4-isothiocyanato-4-methyl-2-pentanone, 2,3-diaminonaphthalene and N-aminoethyladenosine gave in good
yields substituted pyrimidonaphthoimidazole and imidazopyrimidine thione. Refluxing pyrimidobenzthiazole with methanol H2SO4 at pH∼1 resulted in S-methyl pyrimidobenzthiazole in moderate yield. Pyrimidobenzimidazole derivatives could be reacted to S-alkylated
and N-acylated derivatives by refluxing with ethyl bromoacetate in the presence of anhydrous potassium carbonate in THF and by heating in an acetic acid/acetic anhydride mixture. Heating of pyrimidobenzimidazole with 75% aqueous H2SO4 on a water bath ended up in a rearranged product. All compounds gave correct 1H NMR, IR, and HR mass spectra. Results of antiinflammatory, analgesic, and anticancer activity screening of the new compounds
are described.
Received October 29, 1999. Accepted (revised) January 13, 2000 相似文献
Benzoylhydrazone Schiff base–ligated three new ONO pincer–type palladium(II) complexes, [(PdL1(PPh3)] ( 1 ), [(PdL2(PPh3)] ( 2 ), and [(PdL3(PPh3)] ( 3 ), were synthesized by the reaction of the respective ligand, N-(2-hydroxybenzylidene)benzohydrazide (HL1), N-(2-hydroxy-3-methoxybenzylidene)benzohydrazide (HL2), or N-(5-bromo-2-hydroxybenzylidene) benzohydrazide (HL3), with Pd(OAc)2 and PPh3 in methanol and isolated as air-stable reddish-orange crystalline solids in high yields (78%–83%). All three complexes were fully characterized by elemental analysis, Fourier-transform infrared spectroscopy, UV–Visible, 1H nuclear magnetic resonance (NMR), 13C{1H} NMR, and 31P{1H} NMR spectroscopic studies. The molecular structure of all three complexes was established unambiguously by single-crystal X-ray diffraction studies which revealed a distorted square planar geometry of all three complexes. The ONO pincer–type ligands occupied three coordination sites at the palladium, while the fourth site is occupied by the monodentate triphenylphosphine ligand. The catalytic potential of all three complexes was explored in the carbonylative Suzuki coupling of aryl bromides and iodides with arylboronic acids to yield biaryl ketones, using CHCl3 as the source of carbonyl. The reported protocol is convenient and safe as it obviates the use of carbon monoxide (CO) balloons or pressured CO reactors which are otherwise needed for the carbonylation reactions. The methodology has been successfully applied to the synthesis of two antineoplastic drugs, namely, phenstatin and naphthylphenstatin, in good yields (81% and 85%, respectively). Under the optimized reaction conditions, complex 2 exhibited the best catalytic activity in the carbonylative Suzuki couplings. The reported catalysts have wide reaction scope with good functional group tolerance. All catalysts could be retrieved from the reaction after completion and recycled up to three times with insignificant loss in the catalytic activity. 相似文献
Russian Journal of General Chemistry - This study is devoted to the efficient and practical synthesis of a novel series of pyrido[4,3-d]pyrimidine derivatives attached to 1,2,3-triazole ring and... 相似文献
The dissociation of hierarchically formed dimeric triple lithium bridged triscatecholate titanium(IV) helicates with hydrocarbyl esters as side groups is systematically investigated in DMSO. Primary alkyl, alkenyl, alkynyl as well as benzyl esters are studied in order to minimize steric effects close to the helicate core. The 1H NMR dimerization constants for the monomer–dimer equilibrium show some solvent dependent influence of the side chains on the dimer stability. In the dimer, the ability of the hydrocarbyl ester groups to aggregate minimizes their contacts with the solvent molecules. Due to this, most solvophobic alkyl groups show the highest dimerization tendency followed by alkenyls, alkynyls and finally benzyls. Furthermore, trends within the different groups of compounds can be observed. For example, the dimer is destabilized by internal double or triple bonds due to π–π repulsion. A strong indication for solvent supported London dispersion interaction between the ester side groups is found by observation of an even/odd alternation of dimerization constants within the series of n-alkyls, n-Ω-alkenyls or n-Ω-alkynyls. This corresponds to the interaction of the parent hydrocarbons, as documented by an even/odd melting point alternation. 相似文献
40 MeV -particles have been used to determine oxygen impurity at ppm levels in silicon, copper, and stainless steel, through the radiochemical separation of18F from the matrix. The separation of18F has been carried out by two techniques, viz.(1) distillation of H2SiF6 and (2) precipitation of KBF4 and some modification has been applied in the separation, depending on the nature of interferences from the matrix. Instrumental approach was also carried out to determine the oxygen impurity at 100 ppm in Si matrix because this approach is not possible in Cu and stainless steel samples due to matrix activity. 相似文献
Let D ? ?n be a bounded domain with piecewise-smooth boundary, and q(x,t) a smooth function on D × [0, T]. Consider the time-like Cauchy problem Given g, h for which the equation has a solution, we show how to approximate u(x,t) by solving a well posed fourth-order elliptic partial differential equation (PDE). We use the method of quasi-reversibility to construct the approximating PDE. We derive error estimates and present numerical results. 相似文献