Influence of adsorption on the measurement of diffusion coefficients by Taylor dispersion

The effect of adsorption on the measurement of diffusion coefficients by the Taylor dispersion technique is investigated by modifying the governing equation to account for reversible, nonequilibrium adsorption. The resulting two-dimensional equations are solved by an explicit finite-difference technique. Experimental data for the acridine carbon dioxide system indicated that acridine adsorbs on the walls on the tubing and these data were investigated with this model. The influence of carious parameters including the number of sites and the rates of adsorption desorption was investigated by conducting a parametric sensitivity analysis on the model. It was found that adsorption of the solute on the wall of the tubing could produce an error as high as 35% on the measured diffusion coefficient compared to the actual diffusion coellicient. Examination of the influence of each of the parameters will enable Inure investigators to reduce the effect of adsorption in the measurement of diffusion coefficients by Taylor dispersion.     

Kinetics of the enzymatic degradation of poly(vinyl acetate) in solution

The enzymatic degradability of poly(vinyl acetate) was investigated in toluene solutions at various temperatures with hog pancreas lipase. The polymer degraded by specific scission to yield oligomeric products with a molecular weight of 700. Continuous distribution kinetics were used to determine the rate coefficients. The variation of the rate coefficients with the temperature indicated an optimum at 55°C. The p‐toluene sulfonic acid catalyzed degradation of poly(vinyl acetate) was also investigated. The degradation mechanism was random chain scission, and the energy of activation for degradation was determined from the variation of the rate coefficients with the temperature. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2579–2582, 2003     

Elastic properties of As-Sb-Se glasses

Results of measurement of elastic modulii on As-Sb-Se glasses are reported and their composition dependence discussed. The Young’s and the shear modulii lie in the range of 170–210 and 65–80 kb respectively. These values are typical of chalcogenide glasses. For (As, Sb)₄₀Se₆₀ glasses, the modulii increase monotonically with increasing Sb₂Se₃ content. The observed composition dependence of the modulii for the As _x Sb₁₅Se_{85 −x} glasses is examined in terms of the chemically ordered structural units in the glasses.     

Production of soya milk containing low flatulence‐causing oligosaccharides in a packed bed reactor using immobilised α‐galactosidase

Peanut α‐galactosidase was immobilised in calcium alginate beads and used to hydrolyse the flatulence‐causing oligosaccharides, raffinose and stachyose, in soya milk in batch and in packed bed reactor with recycle. The immobilised enzyme exhibited a slightly lower activity than the free enzyme. The activity yield of immobilised α‐galactosidase was 75.1% and the immobilisation yield was 82.6%. Batch hydrolysis using immobilised enzyme at 55 °C resulted in 96% reduction in the oligosaccharides after 12 h. For the continuous process, a packed bed reactor with recycle was used. More than 98% of the oligosaccharides were hydrolysed after 6 h of reaction at 55 °C. The immobilised enzyme also proved to be stable up to three repeated hydrolysis reactions.     

Kinetics of microwave‐assisted polymerization of ϵ‐caprolactone

The kinetics of polymerization of ?‐caprolactone (CL) in bulk was studied by irradiating with microwave of 350 W and frequency of 2.45 GHz with different cycle‐heating periods (30–50 s). The molecular weight distributions were determined as a function of reaction time by gel permeation chromatography. Because the temperature of the system continuously varied with reaction time, a model based on continuous distribution kinetics with time/temperature‐dependent rate coefficients was proposed. To quantify the effect of microwave on polymerization, experiments were conducted under thermal heating. The polymerization was also investigated with thermal and microwave heating in the presence of zinc catalyst. The activation energies determined from temperature‐dependent rate coefficients for pure thermal heating, thermally aided catalytic polymerization, and microwave‐aided catalytic polymerization were 24.3, 13.4, and 5.7 kcal/mol, respectively. This indicates that microwaves increase the polymerization rate by lowering the activation energy. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1450–1456, 2004     

Temperature effects on the transition from nucleation and growth to Ostwald ripening

Condensation, involving nucleation, growth, and ripening from a metastable state, is an important but complex phase transition process. The effect of physical parameters, including temperature, on condensation dynamics, the competition between homogeneous and heterogeneous (seeding) nucleation, and the separation of polymorphs are among several issues of practical interest. We present a model based on population dynamics that describes the time evolution of the particle size distributions for condensation of the fluid phase and consequent decline in supersaturation. The crucial effect of interfacial curvature on energy, and hence on particle size (Gibbs-Thomson effect), causes larger particles to be less soluble, so that smaller particles dissolve and eventually vanish (denucleate). Numerical solutions of the governing equations show the transition from nucleation and growth to ripening occurs over a relatively long time period. The influence of temperature on these phenomena is primarily through its effect on interfacial energy, growth rate coefficients, and equilibrium solubility. Temperature programming is proposed as a potential method to control the size distribution during the phase transition. The model suggests conditions to suppress homogeneous nucleation by seeding. We also explore how a temperature program for cooling crystallization based on different properties of the crystal forms can separate two crystal polymorphs.     

Simultaneous removal of nitrate and arsenic from drinking water sources utilizing a fixed-bed bioreactor system

A novel bioreactor system, consisting of two biologically active carbon (BAC) reactors in series, was developed for the simultaneous removal of nitrate and arsenic from a synthetic groundwater supplemented with acetic acid. A mixed biofilm microbial community that developed on the BAC was capable of utilizing dissolved oxygen, nitrate, arsenate, and sulfate as the electron acceptors. Nitrate was removed from a concentration of approximately 50 mg/L in the influent to below the detection limit of 0.2 mg/L. Biologically generated sulfides resulted in the precipitation of the iron sulfides mackinawite and greigite, which concomitantly removed arsenic from an influent concentration of approximately 200 ug/L to below 20 ug/L through arsenic sulfide precipitation and surface precipitation on iron sulfides. This study showed for the first time that arsenic and nitrate can be simultaneously removed from drinking water sources utilizing a bioreactor system.     

Relaxation of extrinsic and intrinsic stresses in germanium substrates with silicon films

Si films were deposited on Ge substrates at 400°C by two different Physical Vapor Deposition techniques: (A) ion beam sputtering and (B) magnetron sputtering. The intrinsic stresses in the as-deposited films were measured to be compressive and much greater in samples (A), about −1500 to −2000 MPa than in samples (B), about −300 to −500 MPa. The substrates were subsequently exposed to thermal treatments for varying times at 800°C. In the lower stressed (B) samples, the films had relaxed and reduced the overall curvature of the structure whereas in the high stresses (A) samples, an irreversible large increase in the substrate curvature was found to occur. This indicated that plastic deformation in the Ge substrates itself had occurred.