Influence of Cycle Temperatures on the Thermochemical Heat Storage Densities in the Systems Water/Microporous and Water/Mesoporous Adsorbents

The adsorption equilibrium of water on microporous adsorbents (zeolites of NaA-, NaY- and NaX-type as well as their ion exchanged forms) and on mesoporous adsorbents (different silica gels and composite material i.e. silica gel + salt hydrate) has been studied experimentally and theoretically. Using the Dubinin theory of pore filling the characteristic curves of the adsorption systems and other relevant dependences such as isotherms, isobars, isosteres and the curve of the differential heat of adsorption were calculated. For all systems investigated the adsorption were calculated. A_ads and the desorption potential A_des of the closed heat storage system were estimated. These values define the working range of the adsorption/desorption cycle and allow to calculate the specific heat storage density Δ h_sp. On the basis of Δ h_sp the different adsorbents were compared in order to select the optimal porous storage material for a given application. The presented experimental and theoretical investigations show that the adsorption systems water-zeolite and water-composites are promising working pairs for thermochemical heat storage processes for hot tap water supply and space heating of single family dwellings. The advantage of the water-composite system is the low desorption temperature (solar energy) the main shortcoming the low temperature lift. The advantage of the water zeolite system is the high temperature lift, the shortcoming are the relative high desorption temperatures.     

Anaerobic reduction of a sulfonated azo dye, Congo Red, by sulfate-reducing bacteria

The capacity for anaerobic decolorization of a sulfonated azo dye, Congo Red, by a strain of a sulfate-reducing bacterium was evaluated. After optimizing the growth rate of the bacteria on a simple carbon source and terminal electron acceptor pair, lactate and sulfate, respectively, the effect of the dye concentration on their growth rate was analyzed. The decolorization rate was affected by the dye concentration in the growth medium. The azo-bond cleavage mechanism of reductive decolorization with the formation of benzidine was consistent with the results, as this metabolite was identified by high-performance liquid chromatography. Several fractions of the culture medium, including lysed cell extracts, were examined for the capacity to reduce the azo dye. This reduction capacity was found in the culture medium in which the cells had previously grown. The results showed that the mechanism of reductive decolorization of this sulfonated azo dye was extracellular and nonenzymatic, consistent with the production of sulfide anion by the microorganisms while growing on lactate and sulfate. The sulfide anions were the cause of the reduction leading to the disappearance of color in the medium. To increase the rate of decolorization, the presence of ferrous ion was also necessary together with the lactate and sulfate substrates.     

表面引发原子转移自由基聚合方法合成Fe3O4/PMMA复合纳米微粒

采用表面引发原子转移自由基聚合方法合成了核壳结构的磁性高分子纳米微粒. 作为聚合反应引发剂的3-氯丙酸, 首先与油酸修饰的Fe3O4纳米微粒表面的部分油酸置换, 然后在Fe3O4纳米微粒表面引发甲基丙烯酸甲酯聚合, 合成的纳米复合材料用TEM, FTIR, XRD和DSC表征. 磁性测试结果表明, 所制备的磁性高分子纳米微粒仍具有超顺磁性, 但由于聚合物的存在, 其饱和磁化强度降低.     

Nitroxide spin probe study of probe size,hydrogen bonding and polymer matrix rigidity effects on poly(acrylic acid)/poly(ethylene oxide) complexes

An electron spin resonance (ESR) spin probe study was performed on 1 : 1 by weight poly(acrylic acid) (PAA)/poly(ethylene oxide) (PEO) complex over the 100–450 K temperature range with a series of tetramethylpiperidyloxy‐based spin probes. Measurements of the parameters T_5mT, Ta and Td demonstrated the effects of probe size and the strength of hydrogen bonding. The probes in the series Tempone, Tempo, Tempol and Tamine (respectively 4‐oxo‐, unsubstituted, 4‐hydroxy‐ and 4‐amino‐2,2,6,6,‐tetramethylpiperidine ‐1‐oxyl) displayed noticeable increases in the hydrogen‐bonding effect, as indicated by Ta and Td. These increases correlated with increasing hydrogen bond acceptor strength. On the other hand, as the probe size became larger, T_5mT gradually increased due to the free volume decrease. These effects were analyzed using the established theoretical relationship of T_5mT to probe volume expressed by f. Meanwhile, in order to investigate the effect of polymer matrix rigidity, a similar study was performed with a nitroxide spin probe, 2,2,6,6‐tetramethyl‐1‐piperidine‐1‐oxyl (Tempo), on PAA/PEO complexes of different weight compositions. The quantitative fast motion fraction in the composite ESR spectrum was calculated. The influence of changes in the composition of PAA on the molecular mobility was characterized by changes of the spectral parameters and τ_c. The molecular mobility was shown to diminish with increasing content of PAA in PAA/PEO blends duo to the restriction of the polymer matrix rigidity increase. Copyright © 2003 John Wiley & Sons, Ltd.     

Analysis of critical points on the potential energy surface

A simple classification scheme is proposed for critical points, based only on rankr and signatures of the (n,n)-matrixG of harmonic force constants. The determination ofr ands, e.g. by the well-known factorizationG=L ^T gL (L: triangular matrix,g: diagonal matrix), has several theoretical as well as practical (computational) advantages over the inspection of eigenvalues ofG, so far used in quantum chemistry. The eigenvalues are sufficient butnot necessary for a classification whereas rank and signature are the only necessary and sufficient prerequisites for solving the task. For the purpose of presenting a working example, by calculating only a 2×2 torque constant matrix, it is shown that the coplanar ethylbenzene is unstable in the CNDO/2 picture.     

Kinetic study of zirconia crystallization from amorphous ZrO2-SiO2 composite precursors processed by sol-gel chemistry

Powder precursor gels with composition xZrO₂·(100–x)SiO₂, with selected values of x=8, 24, 43 and 75 mol%, were processed by sol-gel chemistry. Differential thermal analysis (DTA) was used to study crystallization in (cubic/tetragonal)-ZrO₂ during the heating of the reactive amorphous precursors. Kinetic parameters such as activation energy, Avrami's exponent and frequency factor have been simultaneously calculated from the computed DTA data using a previously reported kinetic model. The crystallization temperature decreases relative to the increase in the amount of ZrO₂, the value of the kinetic parameter of the crystallization being related to the value of x.     

Oxidation at a sol-gel composite electrode doped with a dirhodium-substituted polyoxometalate for amperometric detection of peptides separated by HPLC

Oxidation of a variety of compounds, including methionine (Met), using a complex formed between dirhodium(II) acetate and the lacunary form of phosphotungstic acid as the catalyst is effective over a wide range of conditions, including pH 2–10. Thus, amperometric detection at a composite in which this complex is immobilized in a sol–gel material does not place restrictions on selection of conditions for separations by reverse-phase HPLC. A demonstration of this point is shown by a study of Met, Met–Phe, Phe–Met, Met–Met, and Gly–Met–Gly (Phe, phenylalanine; Gly, glycine). Using a 0.05 M phosphate buffer at pH 6.7, a C18 column, and a flow rate of 1 ml min⁻¹, capacity factors for Met, Gly–Met–Gly, Met–Met, and Phe–Met were 1.4, 2.1, 5.6, and 34, respectively. Phe–Met and Met–Phe co-eluted.     

A novel composite chitosan membrane for the separation of alcohol-water mixtures

A novel alcohol dehydration membrane with a three layer structure has been prepared. The top layer is a thin dense film of chitosan (CS), and the support layer is made of microporous polyacrylonitrile (PAN). Between the dense and microporous layer, there is an intermolecular cross-linking layer. This novel composite membrane has a high separation factor of more than 8000 and a good permeation rate of 0.26 kg/m² h for the pervaporation of 90 wt% ethanol aqueous solution at 60°C, 0.8 kg/m² h flux for a n-PrOH/water system and around 1 kg/m² h flux for an i-PrOH/water system using 80 wt% alcohol concentration at 60°C. The separation factor for both cases is more than 10⁵. The separation performance varies with feed composition, operating temperature and conditions of membrane preparation. The results show that the separation factor and flux of this membrane increase with raising the operating temperature. At the same time, the crosslinking layer improves durability of the composite membrane, and the pervaporation performance can be adjusted by changing the structure of the cross-linking layer. The cross section of the composite membrane has been examined by SEM.     

An effective cross-linking of polymer layer on monodisperse, poly(maleic anhydride-styrene)-modified colloidal silica particles and properties of the composite

Summary  The cross-linkings of the surface polymer layer on mono disperse, poly(maleic anhydride-styrene)-modified silica particles by the reaction with diisocyanate were studied. The extent of cross-linking was estimated by the weight decrease by immersing the particles in the buffer solution of pH 2.0, 4.0 and 9.0 at a room temperature for 24 h. The reaction of the polymer-modified silica with 1,6-diisocyanatohexane afforded relatively stable composite particles which lost less than 5 wt% of the polymer in aqueous solution in the pH range 2.0–9.0. The diisocyanate was a preferable cross-linker to 2,4-diisocyanatotoluene in terms of stability in acidic or basic aqueous solution. The flexibility of the cross-linker molecule possibly plays an important role in the cross-linking reaction. The carboxyl and amino groups were formed by treating the cross-linked composite particles with diluted HCl solution; 5–6 and 0.5–1.1 μmol g^-1, respectively. The cross-linked composite particles exhibited the characteristic property of ζ-potential, −44 to −47 mV and −102 to −107 mV in a neutral aqueous solution and ethanol, respectively. Received: 26 May 1997 Accepted: 4 August 1997