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941.
Experimental and Theoretical Study of the Effect of Moisture on Methane Adsorption and Desorption by Activated Carbon at 273.5 K 下载免费PDF全文
Adsorption and desorption of methane by activated carbon (AC) at constant temperature and at various pressures were investigated. The effect of moisture was also studied. A volumetric method was used, up to 40 bar, at a temperature of 273.5 K. Results of a dry AC sample were compared with those obtained from a moist sample and two different ACs with different physical and surface properties were used. As expected, the results showed that the existence of moisture, trapped in the AC pores, could lead to a decrease in the amount of methane adsorbed and a decrease in the amount of methane delivered during desorption. To model the experimental results, a large variety of adsorption isotherms were used. The regressed parameters for the adsorption isotherms were obtained using the experimental data generated in the present study. The accuracy of the results obtained from the different adsorption isotherms was favorably compared. 相似文献
942.
Olga?V.?DorofeevaEmail author Igor?F.?Shishkov Lev?V.?Vilkov István?Hargittai 《Structural chemistry》2005,16(6):617-628
The conformational composition of gaseous MTMNB and the molecular structures of the rotational forms have been studied by
electron diffraction at 130∘C aided by results from ab initio and density functional theory calculations. The conformational potential energy surface
has been investigated by using the B3LYP/6-31G(d,p) method. As a result, six minimum-energy conformers have been identified.
Geometries of all conformers were optimized using MP2/6-31G(d,p), B3LYP/6-31G(d,p), and B3LYP/cc-pVTZ methods. These calculations
resulted in accurate geometries, relative energies, and harmonic vibrational frequencies for all conformers. The B3LYP/cc-pVTZ
energies were then used to calculate the Boltzmann distribution of conformers. The best fit of the electron diffraction data
to calculated values was obtained for the six conformer model, in agreement with the theoretical predictions. Average parameter
values (ra in angstroms, angle α in degrees, and estimated total errors given in parentheses) weighted for the mixture of six conformers
are r(C–C) = 1.507(5), r(C–C)ring, av = 1.397(3), r(C–S)av = 1.814(4), r(C–N) = 1.495(4), r(N–O)av = 1.223(3), ∠(C–C–C)ring = 116.0–122.5, ∠ C6–C4–C7 = 118.2(4), ∠ C–C–S = 113.6(6), ∠ C–S–C = 98.5(12), ∠ N–C–C4 = 121.9(3), ∠(O–N–C)av = 116.8(3), ∠ O–N–O = 127.0(4). Torsional angles could not be refined. Theoretical B3LYP/cc-pVTZ torsional angles for the
rotation about C–N bond, φC−N, were found to be 30.5–36.5∘ for different conformers. As to internal rotation about C–C and C–S bonds, values of φC−C = 68–118∘ and φC−S = 66–71∘ were obtained for the three most stable conformers with gauche orientation with respect to these bonds.
Some conclusions of this work were presented in a short communication in Russ. J. Phys. Chem. 2005, 79, 1701. 相似文献
943.
The voltammetric behaviour of chloroquine was investigated at carbon paste and dsDNA-modified carbon paste electrodes in different buffer systems over a wide pH range using cyclic and differential pulse voltammetry. Chloroquine was oxidized in the pH range 2.0-11.0 yielding one irreversible main oxidation peak. A second peak was also observed only in the pH range 5.0-7.0. The modification of the carbon paste surface with dsDNA allowed a preconcentration process to take place for chloroquine such that higher sensitivity was achieved as compared with the bare surface. The response was characterized with respect to solution pH, ionic strength, accumulation time and potential, chloroquine concentration, and other variables. Stripping voltammetric response showed a linear calibration curve in the range 1.0 × 10−7 to 1.0 × 10−5 mol l−1 with a detection limit of 3.0 × 10−8 mol l−1 at the dsDNA-modified electrode. Application of the modified electrode to serum, without sample pretreatment, resulted in good recovery higher than 95% and the higher standard deviation was 3.0%. 相似文献
944.
The molecular structure of trichloronitromethane has been studied in the gas phase using electron diffraction data. The molecules are found to undergo low barrier rotation about the CN bond with a planar CNO2 moiety in agreement with HF/MP2/B3LYP/6-311G(d,p) calculations. The experimental data are consistent with a dynamic model using a potential function for the torsion of V = (V6/2)(1 − cos 6τ). The major geometrical parameters (rg and ) for the eclipsed form, obtained from least squares analysis of the data are as follows: r(NO3) = r(NO4) = 1.213(2) Å, r(CN) = 1.592(6) Å, r(CCl)av = 1.749(1) Å, Cl5CN/Cl6CN = 109. 6°/106.3°(2), O3NC/O4NC = 117. 6°/114.1°(4), τCl5C1N2O3 = 0.0°, and V6 = 0.20(25) kcal/mol. 相似文献
945.
Katalin Mészáros Szécsényi I. Esztelecki G. Pokol 《Journal of Thermal Analysis and Calorimetry》2007,89(3):829-833
In order to increase the nutrition value of bread, one of the most commonly used foodstuff all over the world, different additives
are used in bread processing. In this paper we describe the thermal changes in bread and that of with 0.5% crude soybean lecithin
additive. Their thermal stability has been investigated by TG, DSC and EGD methods. The thermal changes were also followed
of soy products, lecithin and lysine, ingredients used as bread additives in order to check if they may suffer any thermal
degradation during the baking process. The data obtained can be of use only for qualitative conclusions. According to the
obtained data at the usual bread baking temperature only the additives in crust may partly decompose while in the crumb, at
lower temperatures the additives, due to baking, are not damaged. The thermal methods give a possibility for rapid estimation
of processes induced by heat effects in additives during the baking, and they are suitable to detect the changes during the
bread-making procedure. However, they are neither suitable to provide any quantitative data on these changes nor facts affecting
the nutrition value and of the bread. 相似文献
946.
Solubility of lanthanum oxide was measured by thermal analysis. The solubility in alkali cryolites is rather high, because of chemical reactions between lanthanum oxide and cryolites. In Li3AlF6-La2O3, alumina precipitates, in the other systems the mixed oxide LaAlO3 is formed. In La2O3-Li3AlF6 the eutectic point is at 9.5 mol% La2O3 and 755 °C. The eutectic points in La2O3-Na3AlF6 and La2O3-K3AlF6 are at 11.5 mol% La2O3, and at 937 and 934 °C, respectively. 相似文献
947.
G. Schomburg 《Journal of separation science》1979,2(7):461-474
Glass capillary gas chromatography is a high resolution separation method which allows the qualitative and quantitative analysis of even complex mixtures, which may contain many components–also isomeric–in a wide range of volatilities, polarities and concentrations. The principal limitation of gas chromatographic application is given by an insufficient volatility of the species to be separated. Elevated temperatures have to be applied if the application range is to be extended and to achieve steep peak profiles, i.e. low detection limits at high resolution. The use of elevated temperatures is limited, of course, by the temperature stability of both the solvent (stationary liquid and support) and the solutes. The problems of trace analysis for low volatility compounds at high resolution and its limitational parameters regarding sampling, separation and detection are discussed. The applicability of glass capillary columns in this field is influenced by the following parameters: tailing behaviour; irreversible adsorption of polar and decomposition of unstable solutes; thermal stability of stationary liquid (including the support deactivation); separation efficiency and sample capacity (film thickness). Multidimensional gas chromatography using capillary columns coupled either with a packed or another capilllary column for preseparations may be applied with advantage in the analysis of complex mixtures. 相似文献
948.
Poly(propylene adipate) (PPA) and poly(propylene isophthalate/adipate) (PPI-PPA) random copolymers of various compositions were synthesized in bulk and characterized in terms of chemical structure and molecular weight. Furthermore, the thermal behavior was examined by thermogravimetric analysis and differential scanning calorimetry. All the polymers showed a good thermal stability. At room temperature they appeared as semicrystalline materials, except the copolymers containing 20 and 30 mol% of PI units: the main effect of copolymerization was a lowering in the amount of crystallinity and a decrease of melting temperature with respect to homopolymers. The crystalline phase of PPI and PPA was evidenced at high content of propylene isophthalate or propylene adipate units, respectively. Amorphous samples were obtained after melt quenching and an increment of Tg as the content of PI units is increased was observed. This behavior was explained as due to the stiff phenylene groups in the polymeric chain. The Wood equation was found to describe well Tg-composition data. Lastly, the presence of a rigid-amorphous phase was evidenced in the copolymers, differently from PPA homopolymer. 相似文献
949.
Application of vibronic spectroscopy to the conformational analysis of molecules in the ground and excited electronic states is reviewed. The basic concepts of the method as well as its methodological and technical aspects are discussed. The abilities of vibronic spectroscopy are exemplified by the results obtained for molecules of carbonyl compounds.The review is based on a report at the Vibrational Spectroscopy Conference dedicated to the 80th birthday of B. I. Stepanov (Minsk, Belarus', October 3–5, 1993).Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 783–791, May, 1994.This work was performed with the partial financial support of the Russian.Universities State Program. 相似文献
950.
Gololobov Yu. G. Galkin V. I. Petrovskii P. V. Linchenko O. A. Zueva E. M. Mubarakova L. G. Cherkasov R. A. Schmutzler R. Ernst L. Jones P. G. Freytag M. 《Russian Chemical Bulletin》2003,52(9):1920-1927
Studies by 1H NMR spectroscopy and X-ray diffraction analysis revealed hindered rotation of the aromatic substituent about the CAr—N bond in ortho-substituted (except for o-fluorine-substituted) phosphorus-containing carbamates. The energy barriers to rotation (G
c
) and coalescence temperatures (T
c) determined by the coalescence method increase with increasing volume of the ortho substituent. Conformations resulting from rotation of the ortho-substituted aryl group about the CAr—N bond were analyzed by quantum-chemical methods, potential curves were constructed, and differences between the conformational energies and the heights of rotation barriers were estimated. The theoretical rotation barriers change in parallel with the experimental values of G
c
; however, the theoretical values are much smaller in magnitude. 相似文献