The effect of introduction of silica particles prepared by the sol-gel technique on the gas transport properties of a polyimide film was studied. The sorption and permeation of N2, O2, CO2, H2 and CH4 were studied and correlated with morphological changes in the polymer structure. From sorption isotherms, we observed that the composite membrane presents higher solubility coefficients than the polyimide one. The solubility coefficient ratio between the composite and the polyimide is about 1.5–2.0. The isotherms were analyzed in terms of the dual mode sorption. The Henry's coefficient and the Langmuir's affinity and saturation constants were obtained allowing to calculate the Langmuir to Henry concentration ratios as function of the gas pressure. These ratios decrease until zero within a certain pressure range as long as the Langmuir's mode is acting and they are higher for the polyimide membrane when compared with the composite one. This study was completed with calorimetric measurements during the sorption. The gas interaction energy in kJ/mol decreases within the same pressure range as previously described. The measured energies are higher for the polyimide film when compared with the composite one because the polyimide membrane presents a stronger energetic effect caused by a higher Langmuir's contribution. From permeation studies at 3.155 Pa, the composite membrane showed higher permeability coefficients and permselectivities than the polyimide one. All these results were explained, taking into account the difference on the imidization degree of both membranes and the morphological changes which may be induced by the silica nodules in the organic/inorganic interphases. 相似文献
The inclusion complex of benzaldehyde (BA) with β-cyclodextrin (β-CD) was prepared and was studied by thermal analysis and
X-ray diffractometry. The composition of the complex was identified by TG and elemental analysis as β-CD·BA·9H2O. TG and DSC studies showed that the thermal dissociation of β-CD·BA·9H2O took place in three stages: dehydration in the range 70-120°C; dissociation of β-CD·BA in the range 235-270°C; and decomposition
of β-CD above 280°C. The kinetics of dissociation of β-CD·BA in flowing dry nitrogen was studied by means of TG both at constant
temperature and at linearly increasing temperature. The results showed that the dissociation of β-CD·BA was dominated by a
one-dimensional random nucleation and subsequent growth process (A2). The activation energy E was 124. 8 kJ mol-1, and the pre-exponential factor A 5.04·1011 min-1.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
The room temperature wet catalytic oxidation was conducted in a batch reactor with V/MgO catalyst. The XRD study of the catalyst
used indicated that V/MgO could not only oxidize H2S to sulfur selectively, but also prevent the sulfidation of metal oxide
effectively at the room temperature. The XPS study indicated that the H2S oxidation with V/MgO could proceed by a redox mechanism
(V5+↔ V4+) and that V3+ formation (V4+→ V3+), was responsible for the deactivation of V/MgO.
This revised version was published online in June 2006 with corrections to the Cover Date. 相似文献
With frontal analysis(FA),the dependence of adsorption isotherms of insulin on the composition of mobile phase in reversed phase liquid chromatography (RPLC) has been investigated,This is also a good example to employ the stoichiometric displacement theory (SDT) for ivestigating solute adsorption in physical chemistry.Six kinds of mobile phase in RPLC were employed to study the effects on the elution curves and adsorption isotherms of insulin.the key points of this paper are:(1) the stability of insulin due to delay time after preparing,the organic solvent concentration,the kind and the concentration of ion-pairing agent in mobile phase were found to affect both elution curve and adsorption isotherm very seriously.(2)To obtain a valid and comparable result,the composition of the mobile phase employed in FA must be as same as possible to that in usual RPLC of either analytical scale or preparative purpose.(3)Langmuir Equation and the SDT were employed to imitate these obtained adsorption isotherms.The expression for solute adsorption from solution of the SDT was found to have a better elucidation to the insulin adsorption from mobile phase in RPLC. 相似文献
Summary A quantum mechanical calculation of cross sections for the reaction F+H2(v=0,j=0) FH(vj)+H has been performed on the T5A semiempirical potential surface using hyperspherical coordinates. State-to-state integral and differential cross sections converge rapidly with the number of components of the total angular momentum projection onto the axis of least inertia. Thev=3 differential cross section has a forward peak whose magnitude increases with energy whereas thev=2 differential cross section has a backward maximum, in qualitative agreement with cross-beam experiments. Thev=2 andv=3 rotational distributions are in rather good agreement with experiment, but not the vibrational branching ratios. 相似文献
The thermal decomposition of some M
2I
HPO3 (M-Li, Na, K) phosphites under nitrogen atmosphere was investigated. A stepwise mechanism of thermal decomposition has been proposed.
Zusammenfassung Es wurde die thermische Zersetzung von Phosphiten M
2I
HPO3 (M-Li, Na, K) in Stickstoffatmosphere untersucht. Die Schritte des Mechanismus der thermischen Zersetzung wurden vorgeschlagen.
A thin film of manganese hexacyanoferrate (MnHCF) was electrochemically formed on a glassy carbon (GC) electrode to prepare a chemically modified electrode (CME). The mechanism of film formation of MnHCF and its growth process were investigated in detail by cyclic voltammetry. The results show that the stoichiometric composition of MnHCF is Mn^ⅢFe^Ⅲ(CN)6, an analogue of prussian yellow. There exist three clear-cut stages in the whole modification process and the last stage is indispensable to the fabrication of homogenized, stable MnHCF film and must last for an appropriate time. The surface morphology of MnHCF/GC electrode was characterized by scanning electron microscopy (SEM), which further verified the effective deposition of MnHCF film on GC. The kinetic constants of MnHCF/GC electrode process were also evaluated. The resulting MnHCF film modified electrode presented good stability and high electrocatalytic activity toward the oxidation of H2O2, indicating that MnHCF film possesses function of catalase and can be expected for analytical purposes. 相似文献
A complete electrochemical study and a novel electroanalytical procedure for bromhexine quantitation are described. Bromhexine in methanol/0.1 mol L−1 Britton–Robinson buffer solution (2.5/97.5) shows an anodic response on glassy carbon electrode between pH 2 and 7.5. By DPV and CV, both peak potential and current peak values were pH-dependent in all the pH range studied. A break at pH 5.5 in EP versus pH plot revealing a protonation–deprotonation (pKa) equilibrium of bromhexine was observed. Spectrophotometrically, an apparent pKa value of 4.3 was also determined.
An electrodic mechanism involving the oxidation of bromhexine via two-electrons and two-protons was proposed. Controlled potential electrolysis followed by HPLC–UV and GC–MS permitted the identification of three oxidation products: N-methylcyclohexanamine, 2-amino-3,5-dibromobenzaldehyde and 2,4,8,10-tetrabromo dibenzo[b,f][1,5] diazocine.
DPV at pH 2 was selected as optimal pH for analytical purposes. Repeatability, reproducibility and selectivity parameters were adequate to quantify bromhexine in pharmaceutical forms. The recovery was 94.50 ± 2.03% and the detection and quantitation limits were 1.4 × 10−5 and 1.6 × 10−5 mol L−1, respectively. Furthermore, the DPV method was applied successfully to individual tablet assay in order to verify the uniformity content of bromhexine. No special treatment of sample were required due to excipients do not interfered with the analytical signal. Finally the method was not time-consuming and less expensive than the HPLC one. 相似文献