General base catalysis in the decomposition of N-Cl-Valine in aqueous solution

This article analyzes the kinetics of the decomposition of N-Cl-Valine in aqueous solution, which is formed rapidly by chlorination of Valine with sodium hypochlorite. A general-base catalyzed process not yet described is reported. The experimental evidence shows two competitive decomposition paths: an unimolecular concerted fragmentation process (k = (1.8 ± 0.1) · 10^?4 s^?1 at 298 K) and the other one is an E2 elimination process whose importance increases with pH and depends on the nature and the concentration of the bases present in the medium. © 1994 John Wiley & Sons, Inc.     

Temperature-dependent behavior of birefringence and rotation of the optical indicatrix in crystals of deuterated triglycinesulfate

On the basis of a complex null-polarimetric method, the natural birefringence and the rotation of the optical indicatrix in crystals of deuterated triglycinesulfate are measured in the temperature range of 300–340 K. The temperature-dependent behavior of the optical parameters is shown to be close to that observed previously in triglycinesulfate crystals. Changes in them upon the ferroelectric phase transition can be accounted for by the spontaneous quadratic electro-optic effect, with the values of the electro-optic coefficients being larger by a factor of 1.4 than in triglycinesulfate crystals.     

Triangles of Minimal Perimeter Circumscribed about a Convex n-Gon

An algorithm for finding a circumscribed triangle of the minimal perimeter is suggested. Properties of such a triangle are described. Bibliography: 1 title.     

Physical aging of a polyetherimide: Creep and DSC measurements

Creep and differential scanning calorimetry (DSC) measurements have been used to study the physical aging behavior of a polyetherimide. Isothermal aging temperatures ranged from 160°C to T_g with aging times ranging from 10 min to 8 days. The only measurable effect of physical aging on the short-time creep curves is a shift of the creep compliance to longer times. Andrade plots of the compliance versus the cube root of time are linear at short times with the slope β decreasing with increasing aging time to a constant value once equilibrium is reached. Log β³ is related directly to the degree to which the creep curves shift to longer times with physical aging, and is used in this work as a measure of physical aging. A reduced curve of log β³ versus log aging time is obtained for the aging temperatures investigated by appropriate vertical and horizontal shifts. The enthalpy change during aging increases linearly with the logarithm of the aging time, t_a, leveling off at equilibrium at values which increase with decreasing aging temperature. Hence, both nonequilibrium and equilibrium temperature shift factors can be calculated from the DSC data. Good agreement is observed between the equilibrium temperature shift factors obtained from the creep and DSC data. The temperature dependence of the nonequilibrium temperature shift factors is found to be an order of magnitude smaller than that of the equilibrium shift factors. The time scales to reach equilibrium for enthalpy and for mechanical measurements are found to be the same within experimental error. © 1995 John Wiley & Sons, Inc.     

On complementability of certain generalized hypercenters in Artinian modules

We prove that, in an Artinian module, the upper FC-hypercenter over an infinite FC-hypercentral locally solvable group has a direct complement. Thus, we obtain a generalization of one of Zaitsev’s theorems and one of Duan’s theorems.     

Static dust sphere in Einstein-Cartan theory

Physically meaningful solutions of the field equations for static spherical dust distributions in the Einstein-Cartan theory have been obtained. There is one in which the spin is zero at the center and another with zero spin at the boundary of the sphere.     

On the localization of topological invariants

The approach of formal differential geometry to the topological invariants which can be localized is developed. The universal space and universal characteristic forms are constructed. They give rise to primary and secondary characteristic forms.     

The use of sulfide cluster-derived catalysts to understand the promotional effect in hydrotreatment catalysis

Sulfide cluster-derived ensembles are promising models of the active sites in commercial hydrotreatment catalysts. A series of sulfide clusters were adsorbed intact onto high-surface-area γ-alumina, magnesium oxide and activated carbon supports, then pretreated to produce highly dispersed catalytic ensembles with sizes similar to those of their precursor clusters. The activities of the bimetallic cluster-derived catalysts were significantly higher than those of the monometallic catalysts. We took this as evidence that direct interactions between molybdenum and the promoter element cause the promotional effect observed in commercial hydrotreatment catalysts. The hydrodesulfurization and hydrodenitrogenation activities correlated with the extent of molybdenum reduction. Our results suggested that the active sites in promoted hydrotreatment catalysts are centered on molecular-scale ensembles containing molybdenum, sulfur and the promoter element.     

Influence of concentration on the activation energy for diffusion in polymer-solvent systems

The self-diffusion of benzene, toluene, and ethylbenzene in polystyrene have been analyzed using the Vrentas/Duda free-volume diffusion model. Diffusion coefficient predictions suggest an exponential concentration dependence of the activation energy required to overcome attractive forces, E. Without the use of any diffusion data approximating E as zero over the entire concentration range yields self-diffusion coefficient predictions which are in good agreement with experimental data. © 1992 John Wiley & Sons, Inc.