Transition layer thickness in microlaminar deposits

A theoretical analysis was carried out on the change of composition of a deposit obtained by the dual pulse method of forming laminar metal foils, with transition from a low current to a high current pulse, both in the galvanostatic and the potentiostatic mode of deposition. It was shown that the existence of a transition layer of varying composition between a layer of pure metal 1 and a layer consisting predominantly of the metal 2 is an inherent consequence of the electrochemical process, primarily because of an induction period in the concentration polarization with respect to ions of metal 1. The importance of this transition layer increases as the thickness of the layers of the two metals decreases. Eventually this limits the possibility of obtaining a sharp boundary between the layers, when the nanometre region of layer thickness is reached. Equations are given for calculating the deposition current density and rate of stirring of the electrolyte which provide a deposit of a required level of metal 1 in the layer of metal 2, as well as a required sharpness of the boundary between two layers. Experimental proof of the correctness of the analysis was sought. It was found that significant changes in the properties of the deposit occur in the same range of layer thickness in which the transition of the composition takes places.Nomenclature _c,1, a_c,2 transfer coefficient of the cathodic processes - C interfacial capacitance - C₁, C₂ concentration of the ions of metals 1 and 2 at the interface r - C ₀ ¹ , C ₀ ² concentration of ions of the metals 1 and 2 in solution - D ₁ diffusion coefficient for the diffusion of ions of the metal 1 - E _r,1,E _r,2 reversible potentials of metals 1 and 2, respectively - F the Faraday constant - J ₀ ¹ ,J ₀ ² exchange current density of the metals 1 and 2, respectively - M ₁,M ₂ atomic weights of the metals 1 and 2, respectively - kinematic viscosity of solution - ₁, ₂ densities of the metals 1 and 2 respectively - rotation speed (r.p.s.) - z number of electrons exchanged in the deposition process This paper is dedicated to Professor Brian E. Conway on the occasion of his 65th birthday, and in recognition of his outstanding contribution to electrochemistry.     

Secondary ketonization of primary alcohol over LaMn-based mixed oxides with perovskite-like structure

LaMnO₃-based mixed oxides with perovskite-like structure both bulk and supported on La–Al₂O₃, show high catalytic activity in dehydrogenation of n-butanol to an aldehyde, which then undergoes a secondary reaction to produce a symmetrical ketone. Partial substitution of Cu, V or Sr into LaMnO₃ structure does not destroy the perovskite-like structure and enables to control the acid–base surface properties. It allows linking up these qualitative and quantitative features with activity and selectivity of these materials. The degree of n-butanol conversion depends on the total concentration of basic and acidic sites. Selectivity to butyraldehyde can be related with the share of basic sites. Selectivity to dipropyl ketone is affected both by the acidity and concentration of acidic sites. LaMnO₃/La–Al₂O₃ seems to posses an optimum set of surface characteristics for the examined ketonization of a primary alcohol.     

Experimental evaluation of alkaline treatment as a method for enhancing the enzymatic digestibility of autohydrolysed Acacia dealbata

BACKGROUND: Acacia dealbata wood samples were subjected to hydrothermal processing in aqueous media, yielding a liquid phase (containing xylooligosaccharides) and a solid phase, enriched in cellulose, which was treated with alkaline solutions to obtain solids with improved susceptibility towards enzymatic hydrolysis. The effects of the most influential variables involved in the alkaline processing (sodium hydroxide concentration, temperature and reaction time) on solid yield, solid composition and kinetic parameters involved in the modelling of the enzymatic hydrolysis were assessed using the response surface methodology (RSM). RESULTS: Analysis of the RSM equations allowed selection of operational conditions (temperature = 130 °C, sodium hydroxide concentration = 4.5%, time of alkaline processing = 3 h), leading to selective removal of non‐cellulosic components and to a solid substrate highly susceptible to enzymatic hydrolysis. Operating at an enzyme loading of 20 FPU (filter paper units) g^?1 autohydrolysed, extracted solids (denoted AES) with a liquor to solid ratio of 30 g liquor g^?1 AES, solutions containing 29.7 g glucose L^?1 (corresponding to a yield of 47.3 g glucose per 100 g solids from autohydrolysis) were obtained after 48 h. CONCLUSION: Samples of Acacia dealbata wood were processed by autohydrolysis, sodium hydroxide treatment and enzymatic hydrolysis, yielding xylooligomers and processed solids highly susceptible to the enzymatic hydrolysis. Copyright © 2009 Society of Chemical Industry     

APPLICATION OF LINEARIZED MODELS OF MULTICOMPONENT MASS TRANSFER FOR CALCULATION OF EVAPORATION-CONDENSATION PROCESS IN TERNARY SYSTEMS

Results of calculations based on a linearized multicomponent mass transfer theory developed by Burghardt and Krupiczka are compared with experimental data of Modine for condensation-evaporation process in ternary systems. These data have been obtained for acetone-benzene-nitrogen and acetone-benzene-helium in a welted wall column. Models I and II, which take into account diffusional interactions of components in a mullicomponent mixture show good agreement with the experiments as well as with other calculation methods (Krishna-Standart and Toor-Stewart-Prober). When multicomponent mass transfer occurs in the presence of inert species, a straightforward Model II is recommended. Model I, which is more universal, requires some iterative calculations with respect to the sum of mass fluxes. According to theoretical considerations the latter model is limited to the case of low total mass flux. The results of calculations for the systems studied were reasonably good though the total mass fluxes were not small. The calculation procedure based on the presented linearized models are convergent to the proper solutions in contrast to the Krishna-Standart Model IV which in some cases can be unstable.     

Determination of Antioxidant Activity and Polyphenols Content in Chips by Raman and IR Spectroscopy

The application of vibrational spectroscopy for the determination of total polyphenols content, antioxidant activity, colour parameters, and fat level in chips originated from yellow-, red- and purple-fleshed potato varieties is reported. Raman, infrared (IR) and near-infrared (NIR) spectra of the laboratory-prepared chips were collected. Combining spectral data with the results of reference analyses, partial least squares regression models were built. To characterise and compare the elaborated models, the relative standard errors of prediction were calculated for calibration and validation sets. In the case of total phenolics quantification by Raman/IR/NIR techniques, these errors (%) amounted to 4.0/7.0/7.1 and 6.4/8.5/8.4 for calibration and validation samples, respectively, whereas they were 4.9/7.7/4.8 and 6.6/8.3/6.8 for antioxidant activity. The obtained results demonstrate that both infrared and Raman spectroscopy can effectively replace commonly used extraction methods. It follows that Raman spectroscopy has the highest potential to be adopted for the online potato-derived product analysis.     

Moment stability for linear systems with a random parametric excitation

Moment stability for linear systems with a nonwhite parametric noise is considered. A method of reduction of the study of this stability to the study of stability for large-scale matrices is proposed. Mean square stability diagrams for random harmonic oscillator are presented.     

Intermediate moisture food for elder people based on a legume: soybeans, mixture with calcium

An intermediate moisture food (IMF), has been developed in our laboratory for elder people, over 60 years. The IMF is based on a cereal: legume mixture with calcium and flavour, it supplies proteins, carbohydrates and vegetable oils; as well as, high energetic density (3.22 cal/g) and covers up to 51% of calcium needed. It can be easily consumed as a tasty and soft food. It has a water activity of 0.80, for it can be stored at room conditions. It is very likely that IMF becomes a good alternative to improve and vary elder peoples diet.     

A Review on the Radioprotective Activity of organogermanium and Organosilicon Compounds

The present review describes the work carried out during the last 20 years in the field of the radioprotective activity and toxicity of several classes of organosilicon and organogermanium compounds (i.e. metallathiazolidines, metalladithioacetals, metallatranes and germathianes).