95 resultados para Infinite
Resumo:
This paper examines the determinants of unemployment duration in a competing risks framework with two destination states: inactivity and employment. The innovation is the recognition of defective risks. A polynomial hazard function is used to differentiate between two possible sources of infinite durations. The first is produced by a random process of unlucky draws, the second by workers rejecting a destination state. The evidence favors the mover-stayer model over the search model. Refinement of the former approach, using a more flexible baseline hazard function, produces a robust and more convincing explanation for positive and zero transition rates out of unemployment.
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The problem of recognising targets in non-overlapping clutter using nonlinear N-ary phase filters is addressed. Using mathematical analysis, expressions were derived for an N-ary phase filter and the intensity variance of an optical correlator output. The N-ary phase filter was shown to consist of an infinite sum of harmonic terms whose periodicity was determined by N. For the intensity variance, it was found that under certain conditions the variance was minimised due to a hitherto undiscovered phase quadrature effect. Comparison showed that optimal real filters produced greater SNR values than the continuous phase versions as a consequence of this effect.
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Isentropic compressibilities ?S, excess isentropic compressibilities image, excess molar volumes VE, viscosity deviations ??, and excess Gibbs energy of activation of viscous flow ?G*E for nine binary mixtures of C4H8O with CCl4, CHCl3, CHCl2CHCl2, 1-C6H13Cl, 1-C6H13Br, CH3CO2CH3, CH3CO2C2H5, CH3CO2C4H9, and CH3CO2C5H11 at 303.15 K have been derived from experimental densities ?, speeds of sound u, refractive indexes nD and viscosities ?. The limiting values of excess partial molar volumes of C4H8O at infinite dilution image in different solvents have been estimated. The results obtained for dynamic viscosity of binary mixtures were used to test the semi-empirical relations of Grunberg–Nissan, Tamura–Kurata, Hind–McLaughlin–Ubbelohde, Katti–Chaudhri, McAllister, Heric, and Auslaender. Finally, the experimental refractive indexes were compared with the predicted results for Lorentz–Lorenz, Dale–Gladstone, Eykman, Arago–Boit, Newton, Oster, Heller, and Wiener equations.
Resumo:
The ionic nature of ionic liquids (ILs) results in a unique combination of intrinsic properties that produces increasing interest in the research of these fluids as environmentally friendly "neoteric" solvents. One of the main research fields is their exploitation as solvents for liquid-liquid extractions, but although ILs cannot vaporize leading to air pollution, they present non-negligible miscibility with water that may be the cause of some environmental aquatic risks. It is thus important to know the mutual solubilities between ILs and water before their industrial applications. In this work, the mutual solubilities of hydrophobic yet hygroscopic imidazolium-, pyridinium-, pyrrolidinium-, and piperidinium-based ILs in combination with the anions bis(trifluoromethylsulfonyl)imide, hexafluorophosphate, and tricyanomethane with water were measured between 288.15 and 318.15 K. The effect of the ILs structural combinations, as well as the influence of several factors, namely cation side alkyl chain length, the number of cation substitutions, the cation family, and the anion identity in these mutual solubilities are analyzed and discussed. The hydrophobicity of the anions increases in the order [C(CN)3] <[PF6] <[Tf2N] while the hydrophobicity of the cations increases from [Cnmim] <[Cnmpy] [Cnmpyr] <[Cnmpip] and with the alkyl chain length increase. From experimental measurements of the temperature dependence of ionic liquid solubilities in water, the thermodynamic molar functions of solution, such as Gibbs energy, enthalpy, and entropy at infinite dilution were determined, showing that the solubility of these ILs in water is entropically driven and that the anion solvation at the IL-rich phase controls their solubilities in water. The COSMO-RS, a predictive method based on unimolecular quantum chemistry calculations, was also evaluated for the description of the water-IL binary systems studied, where it showed to be capable of providing an acceptable qualitative agreement with the experimental data.
Resumo:
Ionic liquids (ILs) have recently garnered increased attention because of their potential environmental benefits as "green" replacements over conventional volatile organic solvents. While ILs cannot significantly volatilize and contribute to air pollution, even the most hydrophobic ones present some miscibility with water posing environmental risks to the aquatic ecosystems. Thus, the knowledge of ILs toxicity and their water solubility must be assessed before an accurate judgment of their environmental benefits and prior to their industrial applications. In this work, the mutual solubilities for [C2-C8mim][Tf2N] (n-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide) and water between 288.15 and 318.15 K at atmospheric pressure were measured. Although these are among the most hydrophobic ionic liquids known, the solubility of water in these compounds is surprisingly large, ranging from 0.17 to 0.36 in mole fraction, while the solubility of these ILs in water is much lower ranging from 3.2 × 10-5 to 1.1 × 10-3 in mole fraction, in the temperature and pressure conditions studied. From the experimental data, the molar thermodynamic functions of solution and solvation such as Gibbs energy, enthalpy, and entropy at infinite dilution were estimated, showing that the solubility of these ILs in water is entropically driven. The predictive capability of COSMO-RS, a model based on unimolecular quantum chemistry calculations, was evaluated for the description of the binary systems investigated providing an acceptable agreement between the model predictions and the experimental data both with the temperature dependence and with the ILs structural variations.
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Non-ideal behaviour of 1-butyl-3-methylimidazolium hexafluorophosphate [bmim][PF6] in ethylene glycol monomethyl ether; CH3OCH2CH2OH (EGMME), ethylene glycol dimethyl ether; CH3OCH2CH2OCH3 (EGDME) and diethylene glycol dimethyl ether; CH3(OCH2CH2)2OCH3 (DEGDME) have been investigated over the whole composition range at T = (298.15 to 318.15) K. To gain insight into the mixing behaviour, results of density measurements were used to estimate excess molar volumes, image, apparent molar volumes, Vphi,i, partial molar volumes, image, excess partial molar volumes, image, and their limiting values at infinite dilution, image, image, and image, respectively. Volumetric results have been analyzed in the light of Prigogine–Flory–Patterson (PFP) statistical mechanical theory. Measurements of refractive indices n were also performed for all the binary mixtures over whole composition range at T = 298.15 K. Deviations in refractive indices ?phin and the deviation of molar refraction ?xR have been calculated from experimental data. Refractive indices results have been correlated with volumetric results and have been interpreted in terms of molecular interactions. Excess properties are fitted to the Redlich–Kister polynomial equation to obtain the binary coefficients and the standard errors.
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Let H be a (real or complex) Hilbert space. Using spectral theory and properties of the Schatten–Von Neumann operators, we prove that every symmetric tensor of unit norm in HoH is an infinite absolute convex combination of points of the form xox with x in the unit sphere of the Hilbert space. We use this to obtain explicit characterizations of the smooth points of the unit ball of HoH .
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It is proved that for any separable infinite dimensional Banach space X, there is a bounded linear operator T on X such that T satisfies the Kitai criterion. The proof is based on a quasisimilarity argument and on showing that I + T satisfies the Kitai criterion for certain backward weighted shifts T.
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Let M be the Banach space of sigma-additive complex-valued measures on an abstract measurable space. We prove that any closed, with respect to absolute continuity norm-closed, linear subspace L of M is complemented and describe the unique complement, projection onto L along which has norm 1. Using this fact we prove a decomposition theorem, which includes the Jordan decomposition theorem, the generalized Radon-Nikodym theorem and the decomposition of measures into decaying and non-decaying components as particular cases. We also prove an analog of the Jessen-Wintner purity theorem for our decompositions.
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We give an example of a complete locally convex m-topology on the algebra of infinite differentiable functions on [0, 1] which is strictly coarser than the natural Frechet-topology but finer than the topology of pointwise convergence. A similar construction works on the algebra of continuous functions on [0, 1]. Using this examples we can separate different notions of diffotopy and homotopy.
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We prove that for any finite ultrametric space M and any infinite-dimensional Banach space B there exists an isometric embedding of M into B.
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We provide an explicit formula which gives natural extensions of piecewise monotonic Markov maps defined on an interval of the real line. These maps are exact endomorphisms and define chaotic discrete dynamical systems.
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We construct a bounded function $H : l_2\times l_2 \to R$ with continuous Frechet derivative such that for any $q_0\in l_2$ the Cauchy problem $\dot p= - {\partial H\over\partial q}$, $\dot q={\partial H\over\partial p}$, $p(0) = 0$, q(0) = q_0$ has no solutions in any neighborhood of zero in R.
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An example of a sigma -compact infinite-dimensional pre-Hilbert space H is constructed such that any continuous linear operator T: H --> H is of the form T = lambdaI + F for some lambda is an element of R and for a finite-dimensional continuous linear operator F. A class of simple examples of pre-Hilbert spaces nonisomorphic to their closed hyperplanes is given. A sigma -compact pre-Hilbert space H isomorphic to H x R x R and nonisomorphic to H x R is also constructed.