Thermodynamics of continuous media with intrinsic rotation and magnetoelectric coupling

The thermodynamics of an electrically charged, multicomponent continuous medium with intrinsic rotation is analysed in the presence of electromagnetic fields with a weak linear magnetoelectric coupling in the non-relativistic limit. Taking into account the chemical composition of the current densities and stress tensors yields scalar dissipation terms accounting for chemical reactivities and vectorial dissipation terms accounting for transport. Three equations characterising the continuous medium are derived: a thermostatic equilibrium equation, a reversible and an irreversible thermodynamic evolution equation. Explicit expressions for the temperature and the chemical potentials are derived in terms of the electromagnetic fields and the magnetoelectric coupling. The transport equations contain electromagnetic terms normally not included in a standard thermodynamic phenomenology.     

Using Mössbauer spectroscopy to choose the sites that can be occupied by divalent tin

Mössbauer spectroscopy can be a useful structural tool to assist crystallographic methods for site assignment when the compound under investigation contains divalent tin. The goal of this work was to show that the structure of tin(II) fluoride, also know as stannous fluoride, SnF₂, could have been solved 14 years earlier if Mössbauer spectroscopic results, already known, had been used. A first attempt to solve the crystal structure, carried out by Bergerhoff in 1962 seemed to find the tin positions, however, it failed to find the positions of fluorine. Further extensive studies by Dénès et al. in the mid 1970s yielded the same results as those of Bergerhoff, despite the use of a Nonius CAD-4 automatic diffractometer, in contrast with Bergerhoff’s film work. The tin positions yielded a residual of 0.23, and Fourier difference maps showed significant electron density that could be fluorine atoms, however, their number did not match the number of fluorine atoms expected and several F-F distances were way too short. In addition, refinement using these possible fluorine positions led to no improvement of the residual factor. Finally, the crystal structure was published by McDonald et al. in 1976. It was found that the tin sublattice determined by Bergerhoff was basically correct, except that half of the tin atoms found by Bergerhoff to be on the (4b) and (4e) special Wyckoff sites were actually on the (8f) general site. A translation of the origin of the unit-cell by the [1/8, 0, 3/16] vector allows to change the tin Wyckoff sites from (4b), (4e) and (8f) to two (8f) sites, while keeping the basic spatial distribution of tin. A method has now been designed, using ¹¹⁹Sn Mössbauer spectroscopy, to test the suitability of some Wyckoff sites for divalent tin, using the Mössbauer spectrum. The tin(II) doublet (δ = 3.430(3) mm/s, Δ = 1.532(3) mm/s) shows that the lone pair is on a hybrid orbital, therefore, it is stereoactive, and it results that tin cannot be on either the (4b) or (4e) tin site since both an inversion center and a 2-fold axis would generate a second lone pair unless the 2-fold axis were along the tin-lone pair axis.     

Optimal government scrappage subsidies in the presence of strategic consumers

Many countries have introduced vehicle scrappage programs to motivate consumers to replace their old cars earlier. Since these programs are generally offered over a given period of time, policy makers need to plan for inter-temporal subsidies. Considering a two-period game between strategic consumers and the government, we determine the optimal scrappage subsidy levels. Our results demonstrate that the subsidy level in the second period is higher than in the first, allowing the government to discriminate on price (or subsidy) between consumers with different valuations. In addition, we show that subsidy levels increase with the government’s targeted replacement level. However, when the government target level changes from intermediate to high, the first-period subsidy drops while the second-period subsidy remains unchanged.     

The synthesis of a verdazyl radical-derived biphenylophane

Biphenylophanes with two stacked biphenyl units are synthetically challenging and consequently are rare. Herein, we report on the synthesis of a [3.3](3,4′,3,4′)biphenylophane, formed from bifunctional verdazyl radicals. Its formation is surmised to originate from two intermediate verdazyl radical-derived azomethine imines and their subsequent tandem inter-intramolecular 1,3-dipolar cycloaddition reaction with each other.     

Performance study of the multiwavelet discontinuous Galerkin approach for solving the Green-Naghdi equations

This paper presents a multiresolution discontinuous Galerkin (DG) scheme for the adaptive solution of Boussinesq-type equations. The model combines multiwavelet (MW)–based grid adaptation with a DG solver based on the system of fully nonlinear and weakly dispersive Green-Naghdi (GN) equations. The key feature of the adaptation procedure is to conduct a multiresolution analysis using MWs on a hierarchy of nested grids to improve the efficiency of the reference DG scheme on a uniform grid by computing on a locally refined adapted grid. This way, the local resolution level will be determined by manipulating MW coefficients controlled by a single user-defined threshold value. The proposed adaptive multiwavelet DG solver for GN equations is assessed using several benchmark problems related to wave propagation and transformation in nearshore areas. The numerical results demonstrate that the proposed scheme retains the accuracy of the reference scheme, while significantly reducing the computational cost.     

High‐temperature kinetics of the reaction between CN and hydrocarbons using a novel high‐enthalpy flow tube

More than 70 molecules of varied nature have been identified in the envelopes of carbon‐rich stars through their spectral fingerprints in the microwave or far infrared regions. Many of them are carbon chain molecules and radicals, and a significant number are unique to the circumstellar medium. The determination of relevant laboratory kinetics data is critical to keep up with the development of the high spectral and spatial resolution observations and of the refinement of chemical models. Neutral–neutral reactions of the CN radical with unsaturated hydrocarbons could be a dominant route in the formation of cyanopolyynes, even at low temperatures and deserve a detailed laboratory investigation. The approach we have developed aims to bridge the temperature gap between resistively heated flow tubes and shock tubes. The present kinetic measurements are obtained using a new reactor combining a high‐enthalpy source with a flow tube and a pulsed laser photolysis–laser‐induced fluorescence system to probe the undergoing chemical reactions. The high‐enthalpy flow tube has been used to measure the rate constant of the reaction of the CN radical with propane (C₃H₈), propene (C₃H₆), allene (C₃H₄), 1,3‐butadiene (1,3‐C₄H₆), and 1‐butyne (C₄H₆) over a temperature range extending from 300 to 1200 K. All studied reactions of CN with unsaturated hydrocarbons are rapid, with rate coefficients greater than 10^?10 cm³ · molecule^?1 · s^?1 and exhibit slight negative temperature dependence above room temperature. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 44: 753–766, 2012     

A fair and time‐consistent sharing of the joint exploitation payoff of a fishery

We consider the problem of efficiently managing a fishery where pollution externalities are present. The open‐access bionomic model is analyzed in an ‐player differential game framework with two‐state variables, that is, the fish stock and the pollution stock. We characterize the noncooperative feedback‐Nash equilibrium and cooperative solution, and define an egalitarian sharing rule to allocate the joint welfare maximizing payoff over an infinite time horizon, and show that this rule is time consistent. Recommendations for Resource Managers

• ● Cooperation in management of a fishery where pollution externalities are present yields a higher payoff over time as compared to the noncooperative behavior.
• ● The dividend of cooperation can be allocated among the fisherpersons according to an egalitarian sharing rule.
• ● This allocation is time‐consistent, that is, no player will be tempted to deviate from cooperation as time goes by, and the initial agreement is sustainable.

     

Biosensor employing screen‐printed PEDOT:PSS for sensitive detection of phenolic compounds in water

Poly(3,4‐ethylenedioxythiophene) (PEDOT) and its derivatives are relatively new, and unique members of conducting‐polymers family. In this article, we present an approach for simple, reliable and cost‐efficient electrochemical biosensor for real‐time detection and quantification of phenolic compounds (PhCs). The PEDOT:poly(styrene sulfonate) (PSS) polymer, directly screen‐printed on the surface of the working electrode, was shown to act as an effective electrical conductor but also as an efficient redox mediator. It has also been found suitable for the reduction of quinone ions at low reducing potentials, close to 0 V versus Ag/AgCl, thus minimizing interferences due to other electroactive species present in real samples. Based on these properties, a biosensor based on tyrosinase immobilized on PEDOT:PSS‐modified electrodes was developed allowing the detection of PhCs in surface waters. The biosensor displayed very good performance in terms of sensitivity, detection limit and linear range. Assays using surface water previously spiked with bisphenol A showed that the biosensor was able to detect PhCs in real conditions with no matrix effect. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Parameterization of Unstable Manifolds for DDEs: Formal Series Solutions and Validated Error Bounds

Journal of Dynamics and Differential Equations - This paper studies the local unstable manifold attached to an equilibrium solution of a system of delay differential equations (DDEs). Two main...