Temperature dependence of the rate constants for reactions of the carbonate radical with organic and inorganic reductants

Rate constants have been measured by pulse radiolysis for the reactions of the carbonate radical, CO₃^·?, with a number of organic and inorganic reactants as a function of temperature, generally over the range 5 to 80°C. The reactants include the substitution-inert cyano complexes of Fe^II, Mo^IV, and W^IV, the simple inorganic anions SO₃^2?, ClO₂^?, NO₂^?, I^?, and SCN^?, several phenolates, ascorbate, tryptophan, cysteine, cystine, methionine, triethylamine, and allyl alcohol. The measured rate constants ranged from less than 10⁵ to 3 × 10⁹ M^?1 s^?1, the activation energies ranged from ?11.4 to 18.8 kJ mol^?1, and the pre-exponential factors ranged from log A = 6.4 to 10.7. The activation energies for the metal complexes and inorganic anions generally decrease with increasing driving force for the reaction, as expected for an outer sphere electron transfer. For highly exothermic reactions, however, the activation energy appears to increase, probably reflecting the temperature dependence of diffusion. For many of the organic reactants, the activation energies were low and independent of driving force, suggesting that the oxidation is via an inner sphere mechanism.     

Scaling probability, key to the equilibrium statistical volume distribution in foams

The equilibrium statistical volume distribution in foams, which has been previously demonstrated to be the so-called log-normal, is accounted on probability grounds by a scaling law on the bubble's volume time-evolution. This law states that the conditional probability for a given bubble to have the volume v(t + Δt), he assumption that it was v(t), to depend solely on the relationship v(t + Δt)/v(t), and in particular, to be independent of the time t. The theoretical results, however, allow to go further. Indeed, since the time dependece of its parameters (expectation and variance) are given functions of time, only two parameters are necessary to describe completely the foam.     

On worst-case aggregation analysis for network location problems

Network location problems occur when new facilities must be located on a network, and the network distances between new and existing facilities are important. In urban, regional, or geographic contexts, there may be hundreds of thousands (or more) of existing facilities, in which case it is common to aggregate existing facilities, e.g. represent all the existing facility locations in a zip code area by a centroid. This aggregation makes the size of the problem more manageable for data collection and data processing purposes, as well as for purposes of analysis; at the same time, it introduces errors, and results in an approximating location problem being solved. There seems to be relatively little theory for doing aggregation, or evaluating the results of aggregation; most approaches are based on experimentation or computational studies. We propose a theory that has the potential to improve the means available for doing aggregation.This research was supported in part by the National Science Foundation, Grant No. DDM-9023392.     

Evaluation of peroxyoxalate chemiluminescence postcolumn detection of fluphenazine in urine and blood plasma using high performance liquid chromatography

Peroxyoxalate chemiluminescence may be used for sensitive postcolumn detection of phenothiazine analytes separated by high performance liquid chromatography with appropriate optimization of measurement conditions such as solvent, pH and oxalate ester. Detectability of fluorescent analytes by chemical excitation varies greatly, but analytes with low oxidation potentials are generally more readily detected at low levels, as demonstrated for phenothiazines, an important class of fluorescent drugs. Some improvement in detection limits is observed for fluphenazine when chemiluminescence detection is compared to conventional fluorescence detection. Because of the specificity of chemical excitation, fewer interferences from fluorescent impurities in a urine matrix are observed.     

All-fibre optical system for exciting and detecting the vibration of silicon microresonator sensors

An all-fibre optical system for optical interrogation and detection of the vibrations of a silicon microresonator is reported. Metal-coated silicon microresonators are excited by intensity modulated laser light delivered through an optical fibre, while the vibration of the resonators is detected by an optical fibre interferometer. Measurements have shown that an average optical power of 10 μW is sufficient to maintain the flexural vibration of the resonator. When the resonator is used as a pressure sensor, its resonant frequency changes from 62 kHz to 130 kHz as the pressure varies from -0°6 bar to 1 bar (gauge). A silicon resonator with 700 nm aluminium coating functions as a temperature sensor, showing a frequency shift from 262 kHz to 251 kHz when the temperature changes from 25 °C to 80 °C.     

Boundary G/G Theory and Topological Poisson–Lie Sigma Model

We study a boundary version of the gauged WZW model with a Poisson–Lie group G as the target. The Poisson–Lie structure of G is used to define the Wess–Zumino term of the action on surfaces with boundary. We clarify the relation of the model to the topological Poisson sigma model with the dual Poisson–Lie group G ^* as the target and show that the phase space of the theory on a strip is essentially the Heisenberg double of G introduced by Semenov–Tian–Shansky.     

Regenerative energy conversion using oxygen solid electrolytes

A heat machine is studied of regenerative type, based on solid electrolytes with unipolar oxygen conductivity. The achieved specific power is about 0.2 mW/cm². Electrical characteristics are derived as a function of temperature, pressure and gas composition in the working chamber of the converter. Factors which influence the specific power as well as optimal regimes for the functioning of the device are determined.