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.     

Chemistry of miscible polycarbonate–copolyester blends

Blends of polycarbonate and the copolyester based on 1,4-cyclohexanedimethanol and a mixture of terephthalic and isophthalic acids are known to be completely miscible. This study was concerned with various chemical events which may occur in this system, particularly during melt processing. Degradation reactions were studied by both TGA and dilute viscometry techniques, and some indications of component interaction were noted. The residual titanium catalyst from the copolyester formation was found to produce color formation by interaction with phenolic end groups in the polycarbonate and to promote interchange reactions. Both events could be suppressed by deactivation of the residual catalyst with appropriate additives. An indication of the extent of interchange reactions was obtained by following the crystallizability of the copolyester component using differential scanning calorimetry.     

Crystal Structure of Hydrogenated Canola Oil

Journal of the American Oil Chemists' Society - Scanning electron microscopy was used to study the crystal structure of hydrogenated Canola oil. Fixation of the samples was carried out at 10 C...     

Long chain alkanesulfonates and 1-hydroxy-2-alkanesulfonates: Structure and property relations

Even chain sodium alkanesulfonates from the Strecker reaction, odd chain sodium alkanesulfonates from the alkaline decarboxylation of α-sulfo acids, and sodium 1-hydroxy-2-alkanesulfonates from the reduction of esters of α-sulfo acids were compared with respect to Krafft point, critical micelle concentration, detergency and foam height. Sodium alkanesulfonates and crude fusion products from the α-sulfo acids (mixtures of alkanesulfonates of one less carbon atom with a lesser amount of a soap of two less carbon atoms) are more soluble and have better detergent and foaming properties. Sodium 1-hydroxy-2-alkanesulfonates resemble monosodium salts of α-sulfo acids. Alkanesulfonic acids and 1-hydroxy-2-alkane-sulfonic acids obtained from the sodium salts by ion exchange have lower Krafft points and are more readily soluble. The critical micelle concentrations of 1-hydroxy-2-alkanesulfonic acids and α-sulfo acids are nearly the same and about equal to those of alkanesulfonic acids of one less carbon atom. Presented at the AOCS meeting in Toronto, Canada, 1962. A laboratory of the E. Utiliz. Res. & Dev. Div., ARS, U.S.D.A.     

Planar and axially symmetric slow shearing granular flows: a comparative evaluation of assembly evolution incorporating wavelet transforms

We demonstrate the enhanced capacities of our analysis toolset for three-dimensional data. In particular, we provide supporting evidence for some of the conclusions reached in our previous studies of two-dimensional avalanching heaps. Segregation by self-diffusion is shown to take place in three-dimensional assemblies and self-diffusion velocities are shown to be of a comparable order of magnitude to those found in plane-strain situations. The effect on assembly evolution by discrete avalanching of the availability of a third dimension for translation is investigated. The discrete wavelet transform is again shown to be a useful component of the toolset in coupling process variables in the context of the discrete defining events associated with assembly evolution. In particular, we move towards the determination of time constants by correlating wavelet coefficients with a time shift.     

N.m.r. studies on the effect of water on the glass transition of polystyrene

These investigations are concerned with water-polymer interactions in polymer latices. It is known that water can act as a plasticizer for many solid polymers and cause a reduction in the glass transition temperature, T_g, of the amorphous regions. Experiments were carried out to determine whether pulsed n.m.r. techniques could be used to study the T_g of a polymer suspension and hence the influence of water and electrolyte on it. From T₁ and T₂ proton relaxation measurements as a function of temperature on polystyrene latex systems it was shown that the presence of water lowers the T_g of the polymer particles (by about 10°C), the effect being slightly greater in the presence of concentrated electrolyte. The extent of electrolyte penetration into the particles was deduced by studying relaxation as a function of particle diameter in latices containing paramagnetic Mn²⁺ ions. Using simple theories of relaxation and spin diffusion it was concluded that for all but the smallest particles electrolyte penetration is restricted to a very thin shell of the order of 1 nm. These conclusions were supported by the results of similar measurements on PTFE particles.     

Effects of estrogen-induced hyperlipidemia on the erythrocyte membrane in chicks

The effects of estrogen-induced hyperlipidemia on plasma lipid peroxidation, fatty acid composition and osmotic fragility of erythrocytes in chickens were studied. Young male chickens implanted with estrogen for three wk developed a marked hyperlipidemia. Plasma levels of triglyceride, cholesterol and phospholipid were elevated 68-, four- and 24-fold, respectively, over controls. There was also a two-fold increase in plasma lipid peroxidation measured by the thiobarbituric acid test. Vitamin E supplement (1,000 IU/kg diet) reduced the plasma lipid peroxidation to the control level, but had no effect on the plasma lipid content. Estrogen-induced hyperlipidemia resulted in changes in the fatty acid composition of membrane lipids of erythrocytes. The major changes were an increase in oleic acid from 10.0% to 14.2% and a decrease in linoleic acid from 31.3% to 26.0%. The erytrocytes with an altered membrane fatty acid composition were found to have an increased osmotic fragility. It was apparent that there was a direct correlation between the oleic acid content and the osmotic fragility of erythrocytes.     

Studies of microhardness and mar resistance using a scanning probe microscope

Scanning probe microscopy (SPM) is in a period of rapid development. It shows great promise for characterizing coating surfaces. This paper describes modification of an SPM so that it can be used to mar the surfaces of coatings under controlled conditions and to characterize the mars. Mar resistance of coatings is analyzed in terms of a ‘three response, two mechanism model.' The three responses (fracture, elastic, and plastic) can be measured quantitatively using the SPM. Of the three responses, only two (fracture and plastic deformation) are marring mechanisms – elastic deformations recover instantaneously. In some cases mars resulting from plastic deformation may recover slowly with time or with immersion in water; this phenomenon is attributed to viscoelastic creep. Microhardness is also measured with the modified SPM. Some thermoset coatings appear to be substantially harder near their surfaces than in the mass of material, and such materials may respond quite differently to stress applied at different levels near the surface. This finding has important implications for all coating properties that are strongly influenced by the surface. A quantity called ‘micro mar resistance' is defined. It may be useful for comparing different coatings under specified conditions of marring. However, there can be no single quantity that expresses ‘mar resistance' of a coating under all conditions.     

Effect of liquid wetting on catalyst effectiveness in trickle-bed reactors

The liquid in trickle-bed reactors falls in rivulets down over the catalyst particles. Heretofore, studies of the effect of fractional liquid coverage of the outer surface of the particle on reaction rate have ignored the distribution of the rivulets. A model has been developed in this paper for predicting the effect of number and size of the liquid rivulets. The system of equations has been solved numerically for a first order reaction for two types of reactions: a), one where the rate is determined by the reactant concentration in the liquid, and b), a reaction where the rate is controlled by reactant concentration in the gas phase, as in some hydrogenations. The results show that intraparticle concentration profiles are strongly affected by the distribution and size of the rivulets. However, for both types of reactions the overall rate, as measured by an overall effectiveness factor, is not significantly affected. This result is important since it suggests that distribution and size of the liquid rivulets may be safely ignored in evaluating the effect of liquid coverage, or wetting efficiency, on the rate of reaction     

A review of the unique features of HDL apoproteins

The human plasma high density lipoproteins (HDL) are a heterogeneous ensemble of five proteins associated with both neutral and polar lipids. The sequences of all five proteins are known. ApoA-I and apoA-II are the major protein components; apoC-I, apoC-II and apoC-III are the minor protein components. All these apoproteins spontaneously recombine with phospholipids to give stable lipid-protein complexes and freely exchange between the two major HDL subclasses, HDL₂ and HDL₃. In addition, ApoC-I, apoC-II, and apoC-III exchange between HDL and very low density lipoproteins. Furthermore, certain HDL apoproteins are activators for plasma enzymes that are important in lipid metabolism. ApoA-I and apoC-I activate lecithin/cholesterol acyltransferase; apoC-II is an activator of lipoprotein lipase. The regions of apoC-I and apoC-II that are involved in the activation of these enzymes have been localized with synthetic peptides. Studies of synthetic and native fragments of apoA-II, apoC-I, apoC-II, and apoC-III as well as model lipid-binding peptides have identified specific regions with structural features common to lipid-binding proteins. These special properties, which include helical potential, sequences with a critical amphipathic length, and high hydrophobicity of the nonpolar side of the amphipathic helix, are the determinants of HDL structure and metabolism.