REACTION OF LITHIUM DERIVATIVE OF DIETHYL PHENYLMETHANE-PHOSPHONATE WITH KETONES

Abstract

The reaction of the lithium derivative of diethyl ester of phenylmethanephosphonic acid (1-Li) with alkanones, cycloalkanones, alkylaryl and diarylketones 2s-b is studied at -70°C in THF. The corresponding adducts-diethyl esters of l-phenyl-2,2-dialkyl(phenyl)-2-hydroxyethanephosphonic acids 3s-h are isolated, their yields being usually higher at short reaction time. The olefination of 3-Li as well as of 3 (both by thermolysis or in acidic media) proceeds in low degree, while in the case of 3-Na the yields of alkenes 4 are good. The relative configurations of 3b. 31 and 3g are determined by IR and NMR-spectra, as well as by their stereospecific olefination. “Threo”-stereoselectivity of the addition stage of the reaction of 1-Li with 2b, 21 and 2g is observed, the “threo”/“erythro” ratio remaining independent on the reaction time.     

A new method for the determination of the 34S/32S ratio of water-soluble sulphur in soil

A new method for the determination of the ³⁴S/³²S ratio of water-extractable sulphate in soil is described. Soils are extracted directly with deionized water, which is evaporated down. The remaining residue is then rehydrated and transferred to tin cups containing an adsorbent and mixed with an oxygen donor (V₂O₅). Samples are then analysed using a continuous flow isotope ratio mass spectrometer. The new method requires around 10?g soil per determination, compared to much larger amounts (up to kilograms) of soil required for the previous methods. Sample preparation and subsequent analysis is quick and efficient. The method is demonstrated using a number of soils collected from around the world to provide a range of determined δ³⁴S values. The δ³⁴S values of water-extractable sulphur were broadly similar to those of the soil total sulphur.     

对氨基酚络合萃取机理的探讨

对氨基酚络合萃取机理的探讨;对氨基酚; 络合萃取; 萃取机理; 萃取反应热     

Thermal Conductivity of CuSbSe2 and CuBiSe2 in the Solid and Liquid State

Abstract

Thermal Conductivity of CuSbSe₂ and CuBiSe₂ have been studied in the solid and liquid state in a wide range of temperatures. Measurements of thermal conductivity were carried out using the concentric cylinder method which is based on the flow of heat through a cylindrical wall.     

A numerical investigation of the influence of the aspect ratio in three‐dimensional separated flows

The influence of aspect ratio in three‐dimensional, numerical experiments of separated flows is studied in the case of the backward‐facing step at Reynolds numbers 600, 800, and 950. The computational domain is designed as an actual laboratory experiment. The governing equations are the steady state, isothermal, and incompressible Navier–Stokes equations. The expansion ratio of the computational domain is 1:2. The aspect ratio varies from 1:10 to 1:40. The results of the computations focus on the spanwise variations of the length and the strength of the two eddies along the lower and upper wall. It is concluded that both numerical and laboratory experiments should be designed with an aspect ratio of at least 1:20, if only the accuracy of the position of the detachment and the re‐attachment points matters. If the accuracy of the shear‐stress distributions is also taken into account, then an aspect ratio of at least 1:30 should be chosen. Finally, if the magnitudes of the vortex centers are also considered, then only the aspect ratio of 1:40 qualifies for a realization of two‐dimensional flow conditions in the plane of symmetry. This is contrary to the common practice in the field, at least from the side of laboratory experiments, where an aspect ratio of 1:10 is still considered adequate for this purpose. Copyright © 2011 John Wiley & Sons, Ltd.     

Cluster description of water-in-oil microemulsions near the critical and percolation points

The three-component ionic microemulsion system consisting of AOT/water/decane shows an unusual phase behavior in the vicinity of room temperature. The phase diagram in the temperature-volume fraction (of the dispersed phase) plane exhibits a lower consolute critical point at about 40 degrees centigrades and 10% volume fraction. A percolation line, starting from the vicinity of the critical point, cuts across the plane, extending to high volume fraction side at progressively lower temperatures. In this paper we review the evidence that allows to interpret the phase behavior of our system in terms of interacting spherical droplets. We also investigate the dynamics of droplets, below and approaching the critical point by dynamic light scattering. The first cumulant and time evolution of the droplet density correlation function can be quantitatively calculated by assuming the existence of polydispersed fractal clusters formed by the microemulsion droplets due to attraction. The relaxation phenomena observed in an extensive set of measurements of electrical conductivity and permittivity close to percolation is also reviewed and interpreted through the same cluster-forming mechanism, which reproduces the most relevant features of the frequency-dependent complex dielectric constant of this system. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

Frequency domain measurements on Na2B4O7−V2O5 semiconducting glass

Summary Dielectric measurements on Na₂B₄O₇(99.5%)−V₂O₅(0.5%) glass system, in the frequency range 10⁻³ to 10⁴ Hz and temperature range 300 to 500 K, have been carried out. The normalized plots of complex capacitance have shown a single mechanism responsible for conduction for both volume and surface measurements with their close values of activation energies (0.67±0.03) eV and (0.64±0.03) eV, respectively. The low-frequency dispersion (LFD) behaviour has been observed to be perturbed by the presence of more than one competing process. The impedance plots have shown a parallel combination of a capacitor (C) and a resistor (R), with some contribution of a dispersive element due to charge accumulation in the vicinity of the electrodes. The values ofR andC were found to be of the same order of magnitude, for both surface and volume measurements. The observedR has shown a decrease with an increase in temperature due to an increase in mobility of Na⁺ ions, whereasC remains practicaly constant. The complex capacitance surface behaviour is dominated by volume, due to hygroscopy of this glass system.     

Near-i.r. Absorption of H2O and D2O in the liquid and supercooled range

Summary Results are reported on near-i.r. absorption spectra of H₂O and D₂O down to the temperature region of supercooled liquid. No anomalous behaviour is observed when the absorbance at any given frequency is studied as a function of temperature. A critical-exponent behaviour strikingly correlating with that exhibited by transport properties is instead observed when spectral deconvolution methods are used. Results are discussed in relation with current views on water structure, based on molecular-dynamics simulation results and connectivity calculations.

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Riassunto Si riportano risultati sugli spettri di assorbimento i.r. di H₂O e D₂O fino alla regione di temperature del liquido sopraraffreddato. L'andamento dell'assorbanza a frequenza costante in funzione della temperatura non mostra alcuna indicazione di comportamento anomalo. Al contrario, quando gli spettri sono analizzati con metodo di deconvoluzione, si osserva un comportamento di tipo esponente critico, che correla straordinariamente bene con quello mostrato dalle proprietà di trasporto. I risultati sono discussi anche in relazione ai piú recenti modelli di struttura dell'acqua, derivanti dai risultati di simulazione e dai calcoli di connettività.

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Резюме Приводятся результаты для спектров инфракрасного поглощения H₂O и D₂O для температур переохлажденной жидкости. Не обнаружено аномального поведения, когда поглощательная способность при заданной частоте изучается как функция темпетатуры. Напротив, при анализе спектров с помощью спектральных методов конволюции наблюдается поведение типа критической экспоненты, которое коррелирует с поведением, определяемым транспортыми свойствами. Полученные результаты обсуждаются в связи с недавними моделями структуры воды, полученными на основе моделирования молекулярной динамики и нычислений связности.

     

The Heat Kernel on Constant Negative Curvature Space Form

Let M be a n-dimensional simply connected, complete Riemannian manifold with constant negative curvature. The heat kernel on M is denoted by H^M_t(x, y) = H^M_t(r(x, y)), where r(x, y) = dist(x, y). We have the explicit formula of H^M_t(x, y) for n=2, 3, and the induction formula of H^M_t(x, y) for n ≥ 4^{[-1]}. But the explicit formula is very complicated for n ≥ 4. ln this paper we give some simple and useful global estimates of H^M_t(x, y), and apply these estimates to the problem of eigenvalue.     

Nonlinear Diffusion Processes

We study elliptic systems of strongly nonlinear first-order differential equations in complex form on the plane. For such systems we develop the theory of Hilbert boundary value problems which is very much similar to the well-known theory for a holomorphic vector. Systems of nonlinear elliptic equations describe problems of interaction of several nonlinear stationary processes in the diffusive and convective mass and heat transport by hydrodynamic fluid flows.