FT-EPR and HPLC study of the mechanism of 4-chlorophenol photolysis

The mechanism of 4-chlorophenol (4CP) photolysis was investigated with the aid of Fourier Transform Electron Paramagnetic Resonance (FT-EPR) and pulsed-laser photolysis combined with High Performance Liquid Chromatography (HPLC) detection-of stable (diamagnetic) products. With FT-EPR transient free radicals produced by pulsed-laser excitation of solutions of 4CP in alcohols could be identified. Time profiles of the FT-EPR spectra provided information on reaction kinetics and Chemically Induced Dynamic, Electron Polarization (CIDEP) effects. It was found that 4CP photolysis in alcohols leads to the simultaneous formation of the phenoxyl radical and radicals produced by hydrogen abstraction from the solvent. CIDEP patterns establish that these radicals are formed in a reaction sequence involving a triplet state precursor and radical pair intermediate. Results of earlier transient optical absorption measurements indicate that the triplet precursor must be the carbene 4-oxocyclohexa-2,5-dienylidene. This assignment is supported by the finding that photolysis of quinone diazide in a hydrogen-donating solvent gives the same free radical products as those obtained from 4CP. The formation of the phenoxyl radical intermediate accounts for the finding that photolysis of deoxygenated solutions of 4CP in alcohols gives phenol as stable diamagnetic product. By contrast, photolysis of aerated and deoxygenated aqueous solutions of 4CP produces benzoquinone and hydroquinone as primary products, respectively.     

Trace pollutants analysis in soil by a time-resolved laser-induced breakdown spectroscopy technique

The results of a joint experiment of IFAM-Pisa and ENEA-Frascati for the detection of traces of pollutants in soil by a time-resolved laser-induced spectroscopy technique are reported. Using samples of soil with known pollutants' concentration [Geochemical Exploration Reference (GXR) silicate from US Geological Survey], we were able to estimate the sensitivity of this Laser-Induced Breakdown Spectroscopy (LIBS) technique to be of the order of some parts per million for a vast class of metallic pollutants, including extremely dangerous soil pollutants such as copper, lead and chromium.ENEA guest with HC&M fellowship     

Mössbauer spectroscopic study of core and mantle of rattle stones

Mössbauer spectroscopy has been applied to two rattle stones found in the Netherlands, which have been formed under different pedoenvironment conditions in the past. Ultrafine particles of goethite are dominantly present in both core and mantle of these stones. The latter differs in both composition and mean particle size; this is related to the distinct manner of their formation.     

Tracking performance in LHCb

The European Physical Journal C - The tracking system of the LHCb detector has been re-optimised to reduce the amount of material which particles traverse. The different subcomponents involved in...     

Inventory strategies for systems with fast remanufacturing

We describe hybrid manufacturing/remanufacturing systems with a long lead time for manufacturing and a short lead time for remanufacturing. We review the classes of inventory strategies for hybrid systems in the literature. These are all based on equal lead times. For systems with slow manufacturing and fast remanufacturing, we propose a new class. An extensive numerical experiment shows that the optimal strategy in the new class almost always performs better and often much better than the optimal strategies in all other classes.     

A Tandem Queue with Coupled Processors: Computational Issues

In Resing and Örmeci [16] it is shown that the two-stage tandem queue with coupled processors can be solved using the theory of boundary value problems. In this paper we consider the issues that arise when calculating performance measures like the mean queue length and the fraction of time a station is empty. It is assumed that jobs arrive at the first station according to a Poisson process and require service at both stations before leaving the system. The amount of work that a job requires at each of the stations is an independent, exponentially distributed random variable. When both stations are nonempty, the total service capacity is shared among the stations according to fixed proportions. When one of the stations becomes empty, the total service capacity is given to the nonempty station. We study the two-dimensional Markov process representing the numbers of jobs at the two stations. The problem of finding the generating function of the stationary distribution can be reduced to two different Riemann-Hilbert boundary value problems, where both problems yield a complete analytical solution. We discuss the similarities and differences between the two problems, and relate them to the computational aspects of obtaining performance measures.     

A New Modal Lindström Theorem

We prove new Lindstr?m theorems for the basic modal propositional language, and for some related fragments of first-order logic. We find difficulties with such results for modal languages without a finite-depth property, high-lighting the difference between abstract model theory for fragments and for extensions of first-order logic. In addition we discuss new connections with interpolation properties, and the modal invariance theorem. Mathematics Subject Classification (2000): Primary 03B45; Secondary 03C95     

Fluid-fluid phase separation in colloid-polymer mixtures studied with small angle light scattering and light microscopy

Mixtures of colloidal silica spheres and polydimethylsiloxane in cyclohexane with a colloid-polymer size ratio of about one were found to phase separate into two fluid phases, one which is colloid-rich and one which is colloid-poor. In this work the phase separation kinetics of this fluid-fluid phase separation is studied for different compositions of the colloid-polymer mixtures, and at several degrees of supersaturation, with small angle light scattering and with light microscopy. The small angle light scattering curve exhibits a peak that grows in intensity and that shifts to smaller wave vector with time. The characteristic length scale that is obtained from the scattering peak is of the order of a few μm, in agreement with observations by light microscopy. The domain size increases with time as , which might be an indication of coarsening by diffusion and coalescence, like in the case of binary liquid mixtures and polymer blends. For sufficiently low degrees of supersaturation the angular scattering intensity curves satisfy dynamical scaling behavior.