Temperature effects on separate values of adsorption and surface reaction rates by dynamic studies

The study of a three-phase catalytic slurry reactor for SO₂ oxidation on activated carbon has been conducted with a dynamic response technique. The analysis of zero and first temporal moments of the gas for temperatures between 10 and 26°C provides individual measurements of the adsorption, desorption and surface reaction rate constants and their energies of activation. A parallel first-moment analysis was carried out for O₂ adsorption onto carbon to obtain the necessary equilibrium constants for temperatures used in the SO₂-oxidation calculations. With second moment analysis of adsorption data, we find the adsorption kinetic constants with and without reaction are in quantitative agreement. By evaluating the separate temperatu effect on the adsorption/desorption, and surface reaction rates, we conclude that neither step is controlling at temperatures up to 26°C. The values the several kinetic and equilibrium constants agree well with those found by other authors.     

Fracture Induced in Al2O3 Bicrystals by Anisotropic Thermal Expansion

Bicrystals of Al₂O₃ were fabricated to study the effects of thermal expansion anisotropy on fracture in a model system containing one grain boundary. Fractures occurred perpendicular to the directions of maximum tensile stress in bicrystals with thermal expansion coefficient differences as low as 0.31×10⁻⁶⁰C⁻¹ and originated at the boundary, probably in areas of high residual stress associated with pores. Numerical stress analysis of two-dimensional model bicrystal configurations showed that stresses induced by thermal expansion anisotropy are maximal in a region localized along the bicrystal boundary.     

Platinum particle size effect on the oxidative dehydrogenation of aqueous ethanol

The effect of the platinum particle size was investigated for the catalytic oxidative dehydrogenation of aqueous ethanol to ethanal at a temperature of 303 K, an ethanol concentration of 260 mol m^–3, a partial oxygen pressure 60 kPa, a pH of 9, and an ethanal and ethanoate concentration of 20 mol m^–3. A particle size effect on the turnover frequency was observed but only for particle sizes smaller than 2 nm. Hence, the reaction shows a limited structure sensitivity.     

Enzymic adaptations in leaf-feeding insects to host-plant allelochemicals

Herbivorous insects have the capacity to develop behavioral, physiological, and biochemical resistance mechanisms in response to chemical selection pressures. Among natural insect-plant associations, there are several cases of target-site insensitivity to and enhanced metabolism of plant allelochemicals. There are also known instances of physiological defenses such as extra rapid excretion or storage of toxic compounds. Multiple defenses seem to be prevalent in natural insect-plant interactions that involve toxic compounds, possibly reflecting the long time these interactions have had to evolve compared to insect-synthetic insecticide interactions. Synthetic insecticides were introduced about 45 years ago. Until recently they have been used as single-active-component preparations. As such, they have been and are very effective in producing insect populations with enhanced detoxification ability and target-site insensitivity. Most insecticide-resistant insect populations have one major defense mechanism. This feature makes the synthetic insecticides very useful tools for studies of insect defenses against toxic chemicals. Information gained from studies with insecticides can shed light on the capabilities of insects to adapt to toxicants in their environment. In assessing the validity of work with synthetic insecticides for natural systems, the fundamental differences between these substances and allelochemicals, and in their presentation to the insects, must, however, be considered. The prevalence of multiple defenses and reliance on modified physiological processes in natural interactions may reflect different properties of the natural chemicals in being generally highly biodegradable and often less acutely toxic than synthetic insecticides. In many cases, the plant allelochemicals are presented to the insects as mixtures. It is, however, to be expected that pest insects will evolve effective multiple defenses against synthetic insecticides. About 20% of all resistant populations have already developed multiple defenses, in most cases combinations of enhanced metabolism and target-site insensitivity. This implies that current crop protection practices need to be modified to ensure the continued usefulness of synthetic insecticides. To achieve this, it is important to study intensively not only insect-insecticide interactions but also the interactions operating in natural insect-plant associations.     

Surface properties of ZSM-5 modified by phosphorus

Phosphorus modification of ZSM-5 leads to extra framework P⁵⁺ and probably incorporation of +3 valence state of P in the framework. The resulting system has increased Brønsted acidity. Theoretical calculations also favour the postulate that phosphorus in +3 valence state can be incorporated into the lattice.     

Light scattering Rayleigh linewidth measurements on some globular protein solutions

An apparatus previously described for investigating the Rayleigh linewidth of light scattered from macromolecular solutions by means of the optical homodyne technique has been modified so as to obtain the autocorrelation function of the fluctuations in scattered intensity. Its operation is described and some results presented for three commercially obtainable globular proteins: chymotrypsinogen, bovine plasma albumin and urease. Measurements were made in unbuffered 0.2M NaCl aqueous solutions and the diffusion constants, D_20w, found to be 7.4±0.3×10^?7cm²s^?1, 5.8±0.1×10^?7cm²s^?1 and 3.4±0.1×10^?7cm²s^?1 respectively. There was no detectable concentration dependence. In each case the results agreed well with theoretical predictions both as regards angular variation and shape of the autocorrelation function. The effects of polydispersity are discussed.     

Incorporation of surface-modified UHMWPE powders and fibers in tough polyurethane composites

Ultrahigh molecular weight polyethylene (UHMWPE) powder (60 micron diameter) and chopped fiber (6.5 mm length) were surface treated with a blend of reactive gases (fluorine and oxygen.) These powders and fibers were then compounded into a thermoset polyurethane matrix. Surface-treated and control reinforcements are compared at a 10 vol.% loading level. Tensile testing indicates improved stress transfer with surface treatment. Stress transfer is also improved with fibers versus powders. Fracture toughness is characterized by measuring the essential work of fracture, w_e. Surface-treated fiber composites exhibit work of fracture values almost three times the unfilled polyurethane values. Abrasion resistance was also measured. Surface treatment was found to significantly lower wear rates of powder composites. Fiber composites had lower wear rates than powder composites, although surface treatment had little effect. An approximate inverse relationship was found between wear rate and essential work of fracture.     

Analyses of flavor qualities of vegetable oils by gas chromatography

Soybean oil, hydrogenated soybean oil, and corn oil were exposed to fluorescent light for different periods of time to obtain a wide range of flavor qualities. The flavor qualities of these oils were evaluated by sensory and gas Chromatographic methods. Sensory evaluation was conducted using a 10-point hedonic scale to rate overall flavor quality. The sensory panel was made up of 94 members from 8 different laboratories. The correlation coefficients (r) of the flavor scores between sensory evaluation and instrumental analysis for soybean oil, hydrogenated soybean oil, and corn oil were 0.95, 0.97 and 0.97, respectively. These results were very close to the correlation coefficients (r) 0.99, 0.98 and 0.95 obtained from 10 sensory panel members from one specific laboratory.     

Plastic Deformation and the Fracture Surface Energy of Sodium Chloride

A correlation between plastic deformation at crack tips in sodium chloride and the measured value of the fracture surface energy is presented. Plastic deformation can either aid or hinder crack growth, depending on the mode of deformation at the crack tip. If plane-stress deformation occurs, crack motion is hindered by step formation, dislocation generation, and plastic blunting of the crack tip. If plane-strain deformation occurs, crack motion is aided by stress fields that arise from the deformation. The specific surface free energy of sodium chloride, {100} plane, is estimated to be less than 0.37 J/m².