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31.
Study of hexane adsorption in nanoporous MCM-41 silica 总被引:2,自引:0,他引:2
Qiao SZ Bhatia SK Nicholson D 《Langmuir : the ACS journal of surfaces and colloids》2004,20(2):389-395
We study here the adsorption of hexane on nanoporous MCM-41 silica at 303,313, and 323 K, for various pore diameters between 2.40 and 4.24 nm. Adsorption equilibria, measured thermogravimetrically, show that all the isotherms, that are somewhat akin to those of type V, exhibit remarkably sharp capillary adsorption phase transition steps and are reversible. The position of the phase transition step gradually shifts from low to high relative pressure with an increase in the temperature as well as the pore sizes. The isosteric heats of adsorption derived from the equilibrium information using the Clapeyron equation reveal a gradual decrease with increasing adsorbed amount because of the surface heterogeneity but approach a constant value near the phase transition. A decrease in the pore size results in an increase in the isosteric heat of adsorption because of the increased dispersion forces. A simple strategy, based on the Broekhoff and De Boer adsorption theory, successfully interprets the hexane adsorption isotherms for the different pore size MCM-41 samples. The parameters of an empirical expression, used to represent the potential of interaction between the adsorbate and adsorbent, are obtained by fitting the monolayer region prior to capillary condensation and the experimental phase transition simultaneously, for some pore sizes. Subsequently, the parameters are used to predict the adsorption isotherm on other pore size samples, which showed good agreement with experimental data. 相似文献
32.
A kinetic model has been developed for the bulk polymerization of vinyl chloride using Talamini's hypothesis of two-phase polymerization and a new concept of kinetic solubility which assumes that rapidly growing polymer chains have considerably greater solubility than the thermodynamic solubility of preformed polymer molecules of the same size and so can remain in solution even under thermodynamically unfavourable conditions. It is further assumed that this kinetic solubility is a function of chain length. The model yields a rate expression consistent with the experimental data for vinyl chloride bulk polymerization and moreover is able to explain several characteristic kinetic features of this system. Application of the model rate expression to the available rate data has yielded 2.36 × 108l mol?1 sec?1 for the termination rate constant in the polymer-rich phase; as expected, this value is smaller than that reported for homogenous polymerization by a factor of 10–30. 相似文献
33.
Israel Cabasso Suresh K. Sahni David Vofsi 《Journal of polymer science. Part A, Polymer chemistry》1988,26(11):2997-3014
Phosphonic acid ester derivatives of glycerol, D -mannitol, D -sorbitol, pentaerythritol, and dipentaerythritol have been synthesized by transacetalation reactions with diethyl 2,2-diethoxyethylphosphonate. These phosphonated derivatives of polyols and carbohydrates have been esterified to from the corresponding methacrylates. All these compounds have been characterized on the basis of their elemental analysis and spectroscopic (infrared including FT–IR, 1H-, 13C-, 31P-NMR, and mass) methods. Transacetalation reactions with dialkyl 2,2-dialkoxyethylphosphonate lead to the synthesis of 1,3-dioxane derivatives in the case of D -mannitol, pentaerythritol, and dipentaerythritol, whereas a mixture of both 1,3-dioxane and 1,3-dioxolane derivatives is obtained with D -sorbitol and glycerol. The methacrylates of phosphonylated polyol derivatives show the capacity to dissolve and interact with metal salts such as bismuth bromide and uranyl nitrate. Some of the polymers obtained from these monomers have been characterized on the basis of their spectral and thermal (differential scanning calorimetry) properties. 相似文献
34.
The extraction of iron(III) from thiocyanate medium was carried out with a synergic combination of 2,4-pentdione (Hacac) and either triphenyl phosphine oxide (Ph(3) PO) or bis (diphenylphosphinyl) alkanes, Ph(2)P(O)(CH(2))(n).P(O)PH(2) [ligand abbreviation, n: dpeO(2), 2; dpbO(2), 4]. Iron(III) was quantitatively separated from its binary mixture with chromium(III), manganese(III), cobalt(II), nickel(II), zinc(II), cadmium(II), mercury(II), lead(II), magnesium(II) and from steel samples. Copper(II) and silver(I) however, interfered. The percentage extraction was 99.0%. The respective extraction constants, K(HA), K(L) or K(syn), for the extracted species, [Fe(NCS)(acac)(2)(H(2)O)] (HA Hacac), Fe(NCS)(3)L(2) [L b Ph(3)PO, dpeO(2) or dpbO(2)], or Fe(NCS)(acac)(2)L were found to be: K(HA), 1.48 x 10(3), K(L), 1.80 x 10(2) (L Ph(3)PO), 2.02 x 10(2) (L dpeO(2) or dpbO(2)) and K(syn), 1.87 x 10(6) (L Ph(3)PO), 2.56 x 10(6) [L dpeO(2) or dpbO(2)]. 相似文献
35.
We present here a tractable theory of transport of simple fluids in cylindrical nanopores, which is applicable over a wide range of densities and pore sizes. In the Henry law low-density region the theory considers the trajectories of molecules oscillating between diffuse wall collisions, while at higher densities beyond this region the contribution from viscous flow becomes significant and is included through our recent approach utilizing a local average density model. The model is validated by means of equilibrium as well nonequilibrium molecular dynamics simulations of supercritical methane transport in cylindrical silica pores over a wide range of temperature, density, and pore size. The model for the Henry law region is exact and found to yield an excellent match with simulations at all conditions, including the single-file region of very small pore size where it is shown to provide the density-independent collective transport coefficient. It is also shown that in the absence of dispersive interactions the model reduces to the classical Knudsen result, but in the presence of such interactions the latter model drastically overpredicts the transport coefficient. For larger micropores beyond the single-file region the transport coefficient is reduced at high density because of intermolecular interactions and hindrance to particle crossings leading to a large decrease in surface slip that is not well represented by the model. However, for mesopores the transport coefficient increases monotonically with density, over the range studied, and is very well predicted by the theory, though at very high density the contribution from surface slip is slightly overpredicted. It is also seen that the concept of activated diffusion, commonly associated with diffusion in small pores, is fundamentally invalid for smooth pores, and the apparent activation energy is not simply related to the minimum pore potential or the adsorption energy as generally assumed. 相似文献
36.
Kuiry SC Megen E Patil SD Deshpande SA Seal S 《The journal of physical chemistry. B》2005,109(9):3868-3872
This article reports an easy chemical method of synthesizing boehmite nanofibers by a modified sol-gel process involving aluminum isopropoxide precursor. Nanorods of gamma-alumina have been successfully prepared after dehydration of the viscous sol at 600 degrees C for 4 h in air. The boehmite nanofibers and gamma-alumina nanorods were characterized by X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy for surface chemistry and functional groups, scanning electron microscopy, high-resolution transmission electron microscopy with selected area electron diffraction, and energy-dispersed spectroscopy for morphology and structure identification. The length of the boehmite nanofibers was found to be more than 10 mum with a crystalline lattice structure. The mechanism of formation of the boehmite nanofibers included the preferential growth along the longitudinal axis due to interaction between the solvent molecules and the surface OH- groups of hydrogen bonds. It is also suggested that the boehmite nanofibers may have formed due to the inherent instability of the planar structure of the boehmite lattice. The diameter of the gamma-alumina nanorods was found to be less than 10 nm with a varying length in the range of 50-200 nm. Boehmite to gamma-Al2O3 transformation was attributed to the loss of water molecules by internal condensation of protons and hydroxyl ions. 相似文献
37.
K. Suvardhan K. Suresh Kumar D. Rekha K. Kiran B. Jaya Raj P. Chiranjeevi 《Journal of Analytical Chemistry》2007,62(4):336-341
Newly synthesized 2-propylpiperidine-1-carbodithioate (2-PPC) was used for the extraction of Cr(III), Ni(II), and Zn(II) from
various water samples. In the present investigation, the use of a syringe loaded with sorbent for the separation and enrichment
of Cr(III), Ni(II), and Zn(II) prior to their determination by inductively coupled plasma-atomic emission spectrometry (ICP-AES)
was proposed to substitute the batch and column techniques. The described method was compared with the column technique with
respect to fastness, simplicity, recovery, and risk of contamination. The syringe was loaded with 1.0 g of sorbent in order
to retain the analyte elements. Next, 7.0 mL of sample solution (pH 5.0 ± 0.2) was drawn into the syringe in 15 s and discharged
over 15 s. Then, an eluent (3.0 M HCl) was drawn into the syringe and ejected back to desorb the analyte elements. At the
optimum conditions, the percentage recoveries of Cr(III), Ni(II), and Zn(II) were in the range of 94.50 to 99.62% with a standard
deviation (S.D.) of 0.03%. The elements could be concentrated by drawing and discharging several portions of sample successively
and eluting only one time. The detailed study of various interferences proved the method to be highly selective. The risk
of contamination is less than that with the column technique. The method was successfully applied to the determination of
Cr(III), Ni(II), and Zn(II) in spiked and natural water samples. The results obtained are in good agreement with those obtained
by the reported methods at the 95% confidence level.
The text was submitted by the authors in English. 相似文献
38.
The determination of lanthanides by Inductively Coupled Plasma Mass Spectrometry (ICP‐MS) is complicated by several spectral overlaps from M+, MO+ or MOH+ ions formed in the ICP. Especially, it is essential to avoid the spectral interferences from lighter lanthanide and Ba polyatomic ions on middle or heavier lanthanides. To tackle this problem, we have developed a mathematical correction method, which reduces all the spectral overlaps from oxide species of Pr, Nd, Ce and Sm over Gd, Tb, Dy and Ho, and Gd, Tb over Yb and Lu. It can also successfully correct the oxide and hydroxide interference of Ba over Eu. The effectiveness of the proposed the mathematical correction scheme is demonstrated for the USGS Standard Rock samples AGV‐1 and G‐2. The results show that the experimental data obtained by applying the mathematical correction scheme for lanthanides is in good agreement with the reported values, using pneumatic and ultrasonic nebulisation methods, for their ICP‐MS analysis. 相似文献
39.
Suresh K. Sahni 《Transition Metal Chemistry》1979,4(2):73-76
Summary Complexes of 2,6-dipicolinic acid hydrazide, DPH, with ZnII, CdII and HgII have been prepared and characterized by elemental analysis, i.r. and electronic spectra and by electrical conductance measurements. The ligand is terdentate, having coordination sites at two deprotonated amide-nitrogen and pyridine-nitrogen atoms. The ZnII and HgII complexes are pentacoordinate whereas the CdII complexes are hexacoordinate and have trigonal bipyramidal and pseudooctahedral stereochemistries, respectively. The Zn, Cd and Hg ions induce cyclization of DPH complexes upon reaction with-diketones. The complexes of macrocyclic ligands so formed have the same stereochemistries as those of DPH. 相似文献
40.
We study the effect of hard-core repulsion (known as the bus effect) betweenB particles on the reaction-diffusion systemA+BB in the continuous-time random walk model in one dimension with theA particles stationary. We show rigorously that the survival probability of theA particles is asymptotically bounded asC
1lim
t{[–logS(t)]/t
0.5}C
2, whereC
1 andC
2 are constants. We also do simulations to confirm our results. 相似文献