Kinetic model for hydrocarbon-assisted particulate boron combustion

A kinetic model is presented to describe the high temperature (1800 K < T < 3000 K) surface oxidation of particulate boron in a hydrocarbon combustion environment. The model includes a homogeneous gas-phase B/O/H/C oxidation mechanism consisting of 19 chemical species and 58 forward and reverse elementary reactions, multi-component gas-phase diffusion, and a heterogeneous surface oxidation mechanism consisting of ‘elementary’ adsorption and desorption reaction steps. Thermochemical and kinetic parameters for the surface reactions are estimated from available experimental data and/or elementary transition state arguments. The kinetic processes are treated using a generalized kinetics code, with embedded sensitivity analysis, for the combustion of a one-dimensional (particle radius), spherical particle. Model results are presented for the oxidation of a 200 μm boron particle in a JP-4/air mixture at ambient temperatures of 1400 K and 2000 K. These results include temperature and gas-phase species profiles as a function of radial distance and particle burning rates. © 1994 John Wiley & Sons, Inc.     

Gas-phase thermal decomposition of peroxy-N-butyryl nitrate

The gas-phase thermal decomposition rate of peroxy-n-butyryl nitrate (n-C₃H₇C(O)OONO₂, PnBN) has been measured at ambient temperature (296 K) and 1 atm of air relative to that of peroxyacetyl nitrate (CH₃C(O)OONO₂, PAN) using mixtures of PAN (14–19 ppb), PnBN (22–46 ppb), and nitric oxide (1.35–1.90 ppm). The PnBN/PAN decomposition rate ratio was 0.773 ± 0.030. This ratio, together with a literature value of 3.0 × 10^?4 s^?1 for the thermal decomposition rate of PAN at 296 K, yields a PnBN thermal decomposition rate of (2.32 ± 0.09) × 10^?4 s^?1. The results are briefly discussed by comparison with data for other peroxyacyl nitrates and with respect to the atmospheric persistence of PnBN. © 1994 John Wiley & Sons, Inc.     

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.     

Hyperbolic spaces are of strictly negative type

We study finite metric spaces with elements picked from, and distances consistent with, ambient Riemannian manifolds. The concepts of negative type and strictly negative type are reviewed, and the conjecture that hyperbolic spaces are of strictly negative type is settled, in the affirmative. The technique of the proof is subsequently applied to show that every compact manifold of negative type must have trivial fundamental group, and to obtain a necessary criterion for product manifolds to be of negative type.

     

Thermoelectric properties of tin clathrates under hydrostatic pressure

We report the temperature dependence of electrical resistance (R) and thermopower (S) of clathrate Cs₈Sn₄₄ under high pressure up to 1.2 GPa. We observe a reversible gap widening, prominent relaxation effect of R, irreversible increase of |S| under high pressure. We also find that the power factor S²σ (σ: electrical conductivity) reaches a maximum at pressure of 0.3 GPa. Comparison of the experimental results with band structure calculations suggests that the intrinsic vacancy in the clathrate structure of Cs₈Sn₄₄ plays an important role in transport properties under high pressure. Measurements on Cs₈Zn₄Sn₄₂, a clathrate which has defects other than vacancies, are compared with Cs₈Sn₄₄. The results indicate that replacing Sn by Zn has similar effect as the intrinsic vacancy on S.     

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.     

Space–Time Chaos,Critical Phenomena,and Bifurcations of Solutions of Infinite-Dimensional Systems of Ordinary Differential Equations

We study infinite-dimensional systems of ordinary differential equations having applications in some popular and important physical problems. The appearance of infinite-dimensional space–time chaos is considered, namely, the bifurcations and critical phenomena that occur in the phase space of the systems and explain some physical problems are described.     

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.