Non-steady-state model for kinetics of free radical polymerization, 4. Direct thermal initiation

This paper deals with the non-steady-state kinetics of direct thermal initiated polymerization. The initiation is assumed to be a bimolecular reaction of the monomer. The relationship between the radical concentration and the monomer conversion is rigorously derived. In further treatment a few very close approximations are introduced based on the fact that the number of monomer molecules reacting in the initiation step is much less than that consumed in the propagation step for a process producing high polymer, and the value of the rate constant for propagation or chain transfer is much lower than that for chain termination. Expressions for various molecular parameters, such as molecular weight distribution, number-average and weight-average degrees of polymerization, and dispersity, are given. Several numerical examples are provided.     

Significance of fluid regime in biological filtration

A dispersed flow model previously developed to study substrate utilization in unsaturated media was experimentally verified and its practical application was considered. For this purpose, measurements were made using tap water and a synthetic feed solution. The importance of the change in fluid regime as regards to the simultaneous transport and reaction within biological filters were demonstrated. The effect of drop formation and the breakage of liquid jets inside the filters on substrate utilization was also shown.     

Reduction of Stibnite at Moderate Temperature

Reduction of stibnite with hydrogen in the presence of calcium oxide has been experimentally inves-tigated at moderate temperature. The results reveal that the effluent generated in the reduction pro-cess contains much less air-polluting substance H_2S, and that the reaction activation energy is63. 3 kJ/mol. The form of antimony changes considerably when the reaction temperature varies.     

Studies of photoconductivity in β-Apo-8′ carotenal

The photoconductive properties of a carotenoid polyene,β-Apo-8′ carotenal in polycrystalline form has been studied. The growth of the photocurrent shows an overshoot in the growth-time curve before steady state value is attained. This behaviour of photocurrent is proposed to be due to higher value of recombination coefficient than trapping coefficient. From the temperature dependence study it is observed that the steady state photocurrent, at first increases with increase of temperature, attains a maximum at a particular temperatureT _max and then decreases with temperature. TheT _max value agrees with the temperature above and below which steady state photocurrent is attained differently. Monomolecular and bimolecular recombination processes at two temperature regimes are proposed to account for the observed behaviour. The dependence of photocurrent with excitation light intensity and wavelength study provide information on the carrier generation processes. The fast decay of photocurrent have been observed at different temperatures and from this study the decay constant is calculated and it is found to be temperature independent.     

Morphological and kinetics study of PEO/PVC blends

The kinetics of spherulite radial growth and the morphology of the compatible system PEO/PVC have been studied by optical microscopy. The usual spherulite radial growth behaviour has been found for compatible blends with PEO content higher than 70%. For lower composition, distortion of the usual spherulite morphology has been observed; the anomalies have been attributed to partial miscibility of the components.     

Kinetic behaviour of muscle LDH immobilized in nylon tubing

Immobilization was carried out of the lactate dehydrogenase (LDH) from rabbit muscle (EC 1.1.1.27), cross-linked through the bifunctional reactive glutar-aldehyde on to nylon tubing (1 m long, 53cm² internal surface area). Immobilized LDH inactivation kinetics are of first order (t_1/2 = 3·6 years, k = 5·4,e^?4 day^?1 to 5°C). The smaller effect of pH on activity than in the case of LDH in solution can be explained on the basis of limitation to proton diffusion towards the support. A limiting effect to free external diffusion of the substrate towards and products from the support was also observed, an effect which seems to determine the effective kinetic behaviour of immobilized LDH. The apparent optimum temperature is centred around 40°C, observing a clear inactivation (thermal denaturation) above this temperature. In the temperature range studied (10–40°C), the co-existence was seen of a kinetic control accompanied by another control, involving diffusional transport of substrates and products, on the global activity of the immobilized enzyme. This makes the Arrhenius profiles curvilinear. Both graphic and statistical non-linear regression analysis of the kinetic data—rate, v, versus substrate concentration [S]—carried out under conditions in which the diffusional limitations can be considered negligible (high recirculation flow rate), permitted investigation of the intrinsic kinetic behaviour of immobilized LDH. In this sense, it can be deduced that the rate equation to which these data seem to be fitted is of the polynomial quotient type in [S] of minimum degree 2:2. Although the diffusional limitations have a marked effect on the type of global kinetics shown by immobilized LDH, temperature was not found to affect its v[S] behaviour. The experimental evidence obtained thus indicates that the rate equation in the 10-40°C temperature range continues to be a rational equation of at least degree 2:2 in [S].     

Vinyl acetate monomer—a pilot plant study

The kinetics of the reaction of acetic acid and acetylene over zinc acetate-activated carbon catalyst was investigated over a wide range of process variables in a pilot reactor. Although various catalytic reaction mechanisms were postulated, the rate of reaction was most satisfactorily correlated by a mechanism of surface reaction between charged adsorbed acetic acid and acetylene, which assumes that the rate controlling step was the irreversible charged adsorption of acetylene and acetic acid.     

Development and characterization of magnetorheological polymer gels

Magnetorheological materials have been used in many applications in recent years. To develop new materials, polyurethane and silicone polymer gels were investigated. Rheology is qualitatively controlled for each system by controlling the concentration of reactants and diluents. The resulting polymers have solid, gel, or liquid states, depending on the crosslinking and dilution. The gels were characterized through kinetic analysis. Differential scanning calorimetry (DSC) was used with analysis methods to find the kinetic properties for diluted and undiluted polyurethane systems. Heat of reaction, order of reaction, preexponential constant, and activation energy were obtained from the experimental DSC data. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2733–2742, 2002     

Screening of supports for the immobilization of pectinmethylesterase from acerola (Malpighia glabra L)

A partially purified extract of pectinmethylesterase (PME) from acerola fruit was immobilized on various supports: glass, celite, chrysotile, agarose, concanavalin A Sepharose 4B, egg shell, polyacrylamide and gelatin. In addition, reticulation with glutaraldehyde was assessed, as well as the use of gelatin in the presence of celite, glass and silica. The highest immobilization yields were obtained when the pectinmethylesterase was immobilized in concanavalin A Sepharose 4B (81.7%) and in gelatin‐water (78.0%). Copyright © 2004 Society of Chemical Industry     

环氧乙烷合成乙二醇的研究进展

介绍了环氧乙烷合成乙二醇的主要生产方法，包括以壳牌、联碳化学公司以及Halcon—SD公司为代表的环氧乙烷直接水合法，环氧乙烷催化水合法和碳酸乙烯酯法，后两种乙二醇生产方法是目前国内外研究开发的热点。催化剂体系是催化水合法工艺的关键，重点介绍了国内外各主要公司对催化剂体系的研究进展及使用效果；碳酸乙烯酯法分为乙二醇和碳酸二甲酯联产法以及碳酸乙烯酯水解法，详细介绍了国内外各主要公司对该技术的研究进展，包括工艺流程、催化剂体系等方面。将3种乙二醇生产方法进行技术经济比较，结果表明，催化水合法和碳酸乙烯酯法在原料消耗和能耗方面占优势。并对我国乙二醇生产工艺技术提出建议。