Measurements of climatic parameters and ground-level ozone at Terra Nova Bay in Antarctica

Summary The results of local meteorology, solar radiation and ground-level ozone measurements taken in Antarctica during the second Italian expedition (December 86–February 87) at Terra Nova Bay are presented. During the summer months the site of the Italian base camp is characterized by a thin strip of deglaciated ground, along which the temperature measurements close to the ground and up to 6 m high show a strongly superdiabatic profile. This irregular trend of the temperature in the surface layer is mainly due to the notable incoming amounts of radiation and to the extreme transparency of the atmosphere. This is also shown by the low values of the ratio between total radiation and diffuse radiation. The ground is thus subjected to intense heating, especially in the warmer hours of the day, while the surface layer of the atmosphere will be characterized by strong upward heat fluxes and by turbulent convective movements. Vertical-temperature-profile measurements show an almost forced persistence in the superdiabatic trend, which tends towards isothermic values only as a resultof rapid variations in the direction and intensity of the wind, connected to the downward flux of cold air masses, shown also by the simultaneous increases in ground-level ozone concentrations which would support the presence of dry-deposition processes in the lower layer. However, the complex local orography and the horizontal discontinuity (sea, deglaciated coast, snow-covered surfaces) do not permit a correct application of profile flux relations, normally used in studies on groundlevel dry-deposition. Paper presented at the IV Congresso del Gruppo Nazionale per la Fisica dell'Atmosfera e dell'Oceano, June 22–24, 1987, Rome.     

Straightforward conversion of alcohols into dibenzenesulfonimides

The reaction of various alcohols with N-fluorodibenzenesulfonimide and triphenylphosphine leads to the corresponding dibenzenesulfonylated amines in high yields.     

Mg 2p shallow core-level and local atomic structure of i-ZnMgRE quasicrystals

We present a detailed analysis of the Mg 2p shallow core-levels measured on icosahedral single-grain ZnMgY, ZnMgHo, and ZnMgEr quasicrystals during a photoelectron microscopy study. The synchrotron radiation photoemission measurements were performed on in situ cleaved samples at a pressure of 10⁻¹⁰ mbar and at low temperature, typically 90-150 K. The Mg 2p photoemission lines are essentially broadened as compared to those of the Mg 2p spin-orbit doublet recorded on the Zn₂Mg crystalline Laves phase. The broadening is associated to the coordination shifts of the Mg 2p level due to the inequivalent magnesium sites in the quasicrystalline lattice. The coordination shifts are calculated on the basis of i-ZnMg(Ho, Y) atomic structure data, recently determined from the pair distribution function analysis. The coordination shifts obtained are up to 0.2 eV. The Mg 2p experimental spectral intensity is nicely reproduced by a superposition of coordination-shifted Mg 2p spin-orbit doublets.     

10.1007/s10955-006-9040-z

We derive hydrodynamic equations describing the evolution of a binary fluid segregated into two regions, each rich in one species,which are separated (on the macroscopic scale) by a sharp interface. Our starting point is a Vlasov-Boltzmann (VB) equation describing the evolution of the one particle position and velocity distributions, f_i (x, v, t), i = 1, 2. The solution of the VB equation is developed in a Hilbert expansion appropriate for this system. This yields incompressible Navier-Stokes equations for the velocity field u and a jump boundary condition for the pressure across the interface. The interface, in turn, moves with a velocity given by the normal component of u.     

Performance analysis of 1300 nm SLEDs – impact of temperature and length scaling

The impact of self-heating and cavity length on the spectral emission properties of SLEDs is investigated using a state-of-the-art simulation tool. Simulated data are compared to measurements for two InP-based benchmark devices operating around 1300 nm, and excellent agreement is achieved in either case.     

Study of correlation holes. I. Number–sum rules and infinite system

The correlation holes in a finite system of any size are known to satisfy integral number–sum rules directly related to the N-representability of the reduced density matrices. In regard to infinite systems, the same rules are known to be satisfied in the electron gas. It is shown that the number–sum rules are not generally satisfied in any infinite system, and that this happens independently of the kind of boundary conditions assumed in the N → ∞ limit. A violation is explicitly found within the alternant molecular orbital formalism. The apparent paradox is explained in terms of surface effects (end effects in a linear system), which are present in a large, but finite system. In other words the N-representability does not imply the number–sum rules. In the N → ∞ limit the rules are satisfied only in physical systems having short-range correlation.     

Anodic stripping voltammetry of sulphide at a nickel film: towards the development of a reagentless sensor

The determination of sulphide at an electrochemically generated nickel oxide layer at glassy carbon and screen-printed electrodes in acidic media has been examined and appraised. The NiO layer was found to produce a stripping-like signal to sulphide and gave a linear peak current response from 20 to 90 μM. The response was further enhanced by repetitive cycling allowing accumulation of nickel sulphide at the electrode surface such that lower micromolar levels of sulphide (i.e. 5 μM) can be determined. The response at the NiO layer to sulphide is shown to be reproducible over a period of 24 h, thereby offering the development of a disposable amperometric sensor for sulphide.     

Determination of ammonia based on the electro-oxidation of hydroquinone in dimethylformamide or in the room temperature ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

The results detail a novel methodology for the electrochemical determination of ammonia based on its interaction with hydroquinone in DMF. It has been shown that ammonia reversibly removes protons from the hydroquinone molecules, thus facilitating the oxidative process with the emergence of a new wave at less positive potentials. The analytical utility of the proposed methodology has been examined with a linear range from 10 to 95 ppm and corresponding limit-of-detection of 4.2 ppm achievable. Finally, the response of hydroquinone in the presence of ammonia has been examined in the room temperature ionic liquid 1-ethyl-3-methylimidazolium bis(trifluormethylsulfonyl)imide, [EMIM][N(Tf)₂]. Analogous voltammetric waveshapes to that observed in DMF were obtained, thereby confirming the viability of the method in either DMF or [EMIM][N(Tf)₂] as solvent.     

Glycidol syntheses and valorizations: Boosting the glycerol biorefinery

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High-pressure dissociation of crystalline para-diiodobenzene: optical experiments and Car-Parrinello calculations

We have investigated the high-pressure properties of the molecular crystal para-diiodobenzene, by combining optical absorption, reflectance, and Raman experiments with Car-Parrinello simulations. The optical absorption edge exhibits a large red shift from 4 eV at ambient conditions to about 2 eV near 30 GPa. Reflectance measurements up to 80 GPa indicate a redistribution of oscillator strength toward the near-infrared. The calculations, which describe correctly the two known molecular crystal phases at ambient pressure, predict a nonmolecular metallic phase, stable at high pressure. This high-density phase is characterized by an extended three-dimensional network, in which chemically bound iodine atoms form layers connected by hydrocarbon bridges. Experimentally, Raman spectra of samples recovered after compression show vibrational modes of elemental solid iodine. This result points to a pressure-induced molecular dissociation process which leads to the formation of domains of iodine and disordered carbon.