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.     

SOME GENERAL EFFECTS OF STRONG HIGH-FREQUENCY EXCITATION: STIFFENING, BIASING AND SMOOTHENING

Mechanical high-frequency (HF) excitation provides a working principle behind many industrial and natural applications and phenomena. This paper concerns three particular effects of HF excitation, that may change the apparent characteristics of mechanical systems: (1) stiffening, by which the apparent linear stiffness associated with an equilibrium is changed, along with derived quantities such as stability and natural frequencies; (2) biasing by which the system is biased towards a particular state, static or dynamic, which does not exist or is unstable in the absence of the HF excitation; and (3) smoothening, referring to a tendency for discontinuities to be effectively “smeared out” by HF excitation. Illustrating first these effects for a few specific systems, analytical results are provided that quantify them for a quite general class of mechanical systems. This class covers systems that can be modelled by a finite number of second order ordinary differential equations, generally non-linear, with periodically oscillating excitation terms of high frequency and small amplitude. The results should be useful for understanding the effects in question in a broader perspective than is possible with specific systems, for calculating effects for specific systems using well-defined formulas, and for possibly designing systems that display prescribed characteristics in the presence of HF excitation.     

LIDAR mapping of ozone-episode dynamics in Paris and intercomparison with spot analyzers Supplementary material available at http://link.springer.de/journals/apb

Continuous mapping of an ozone episode in Paris in June 1999 has been performed using a differential absorption lidar system. The 2D ozone concentration vertical maps recorded over 33 h at the Champ de Mars are compiled in a video clip that gives access to local photochemical dynamics with unprecedented precision. The lidar data are compared over the whole period with point monitors located at 0-, 50-, and 300-m altitudes on the Eiffel Tower. Very good agreement is found when spatial resolution, acquisition time, and required concentration accuracy are optimized. Sensitivity to these parameters for successful intercomparison in urban areas is discussed. Received: 11 February 2002 / Published online: 14 March 2002     

Aspects of the transpiration model for aerofoil design

Transpiration is a technique in which extra non-physical normal flows are created on an aerofoil surface in order to form a new streamline pattern such that the surface streamlines no longer follow the aerofoil surface under inviscid flow. The transpiration model is an important technique adopted in aerofoil design either to avoid mesh regeneration when aerofoil profile co-ordinates are adjusted or to find shape corrections in inverse design methods. A first-order approximation (with respect to the normal streamline displacement) to the transpiration model is commonly adopted; it is shown that this can be a poor approximation especially in regions of high curvature. In this paper more accurate approximations are developed to address this problem and improve the accuracy.     

The effects of flow split ratio and flow rate in manifolds

This paper reports a combined experimental and numerical investigation of three-dimensional steady turbulent flows in inlet manifolds of square cross-section. Predictions and measurements of the flows were carried out using computational fluid dynamics and laser Doppler anemometry techniques respectively. The flow structure was characterized in detail and the effects of flow split ratio and inlet flow rate were studied. These were found to cause significant variations in the size and shape of recirculation regions in the branches, and in the turbulence levels. It was then found that there is a significant difference between the flow rates through different branches. The performance of the code was assessed through a comparison between predictions and measurements. The comparison demonstrates that all important features of the flow are well represented by the predictions.     

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.