995 resultados para Dispersive liquid-liquid microextraction
Resumo:
The simple quasi-steady analysis of the combustion of a liquid fuel droplet in an oxidising atmosphere provides unsatisfactory explanations for several experimental observations. It's prediction of values for the burning constant (K), the flame-to-droplet diameter ratio ( ) and the flame temperature (Tf) have been found to be amgibuous if not completely inaccurate. A critical survey of the literature has led us to a detailed examination of the effects of unsteadiness and variable properties. The work published to date indicates that the gas-phase unsteadiness is relatively short and therefore quite insignificant.A new theoretical analysis based on heat transfer within the droplet is presented here. It shows that the condensed-phase unsteadiness lasts for about 20â??25% of the total burning time. It is concluded that the discrepancies between experimental observations and the predictions of the constant-property quasi-steady analysis cannot be attributed either to gas-phase or condensed-phase unsteadiness.An analytical model of quasi-steady droplet combustion with variable thermodynamic and transport properties and non-unity Lewis numbers will be examined. Further findings reveal a significant improvement in the prediction of combustion parameters, particularly of K, when consideration is given to variations of cp and λ with the temperature and concentrations of several species. Tf is accurately predicted when the required conditions of incomplete combustion or low ( ) at the flame are met. Further refinement through realistic Lewis numbers predicts ( ) meaningfully.
Resumo:
For five binary liquid systems CS2+CH3CN, CS2+CH3NO2, CS2+(CH3CO)2O, C6H12+(CH3CO)2O, n-C7H16+(CH3CO)2O, the electrical resistance has been measured near the critical solution temperatures. The behaviour is universal. Below Tc, the conductivities of the two phases follow σ1−σ2 β, where = T−Tc Tc with β≈0.35. In the one phase region with b≈0.35±0.1 and is positive in some cases and negative in others.
Resumo:
Scaling relations between the critical indices are derived for two similar systems exhibiting λ lines: binary liquid systems and ferromagnets under pressure. In addition to the usual scaling relations, this procedure gives information about other weakly divergent quantities like isothermal compressibility and thermal expansion. Suggestions for more detailed investigations are made.
Resumo:
The system CS2 + CH3NO2 shows β=0.315±0.004 over 10-6<ε=|T-Tc| / Tc<2-10-1 with no indication of a classical value ½ even far away from Tc. The diameter shows a curvature and is of the form - c+b ε+fε7 / 8exp(-gεh).
Resumo:
A rate equation is developed for the liquid-phase oxidation of propionaldehyde with oxygen in the presence of manganese propionate catalyst in a sparged reactor. The equation takes into account diffusional limitations based on Brian's solution for mass transfer accompanied by a pseudo m-. nth-order reaction. Sauter-mean bubble diameter, gas holdup, interfacial area, and bubble rise velocity are measured, and rates of mass transfer within the gas phase and across the gas-liquid interface are computed. Statistically designed experiments show the adequacy of the equation. The oxidation reaction is zero order with respect to oxygen concentration, 3/2 order with respect to aldehyde concentration, and order with respect to catalyst concentration. The activation energy is 12.1 kcal/g mole.
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The adsorption of proteins at the interface between two immiscible electrolyte solutions has been found to be key to their bioelectroactivity at such interfaces. Combined with interfacial complexation of organic phase anions by cationic proteins, this adsorption process may be exploited to achieve nanomolar protein detection. In this study, replica exchange molecular dynamics simulations have been performed to elucidate for the first time the molecular mechanism of adsorption and subsequent unfolding of hen egg white lysozyme at low pH at a polarized 1,2-dichloroethane/water interface. The unfolding of lysozyme was observed to occur as soon as it reaches the organic−aqueous interface,which resulted in a number of distinct orientations at the interface. In all cases, lysozyme interacted with the organic phase through regions rich in nonpolar amino acids, such that the side chains are directed toward the organic phase, whereas charged and polar residues were oriented toward the aqueous phase. By contrast, as expected, lysozyme in neat water at low pH does not exhibit significant structural changes. These findings demonstrate the key influence of the organic phase upon adsorption of lysozyme under the influence of an electric field, which results in the unfolding of its structure.
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The NMR spectra of 2-fluoropyridine in two nematic liquid crystal solvents have been investigated. The direct dipole-dipole coupling constants thus derived have been used to obtain the structural information. The values of the interproton distance ratios arc found to be similar to those in pyridine. The results indicate negligible anisotropic contributions of lH-l9F indirect couplings.
Resumo:
This work presents a numerical analysis of simultaneous mould filling and phase change for solidification in a two-dimensional rectangular cavity. The role of residual flow strength and temperature gradients within the solidifying domain, caused by the filling process, on the evolution of solidification interface are investigated. An implicit volume of fluid (VOF)-based algorithm has been employed for simulating the free surface flows during the filling process, while the model for solidification is based on a fixed-grid enthalpy-based control volume approach. Solidification modeling is coupled with VOF through User Defined Functions developed in the commercial computational fluid dynamics (CFD) code FLUENT 6.3.26. Comparison between results of the conventional analysis without filling effect and those of the present analysis shows that the residual flow resulting from the filling process significantly influences the progress of the solidification interface. A parametric study is also performed with variables such as cooling rate, filling velocity and filling configuration, in order to investigate the coupled effects of the buoyancy-driven flow and the residual flow on the solidification behavior.
Resumo:
The coexistence curve of the binary liquid mixture n-heptane-acetic anhydride has been determined by the observation of the transition temperatures of 76 samples over the range of compositions. The functional form of the difference in order parameter, in terms of either the mole fraction or the volume fraction, is consistent with theoretical predictions invoking the concept of universality at critical points. The average value of the order parameter, the diameter of the coexistence curve, shows an anomaly which can be described by either an exponent 1 - a, as predicted by various theories (where a is the critical exponent of the specific heat), or by an exponent 20 (where P is the coexistence curve exponent), as expected when the order parameter used is not the one the diameter of which diverges asymptotically as 1 - a.
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Glass transition and relaxation of the glycerol-water (G-W) binary mixture system have been studied over the glycerol concentration range of 5-85 mol% by using the highly sensitive technique of electron spin resonance (ESR). For the water rich mixture the glass transition,sensed by the dissolved spin probe, arises from the vitrified mesoscopic portion of the binary system. The concentration dependence of the glass transition temperature manifests a closely related molecular level cooperativity in the system. A drastic change in the mesoscopic structure of the system at the critical concentration of 40 mol is confirmed by an estimation of the spin probe effective volume in a temperature range where the tracer reorientation is strongly coupled to the system dynamics.
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One-dimensional (1D) proton NMR spectra of enantiomers are generally undecipherable in chiral orienting poly-gamma-benzyl-L-glutamate (PBLG)/CDCl3 solvent. This arises due to large number of couplings, in addition to superposition of spectra from both the enantiomers, severely hindering the H-1 detection. On the other hand in the present study the benefit is derived front the presence of several couplings among the entire network of interacting protons. Transition selective 1D H-1-H-1 correlation experiment (1D-COSY) which utilizes the Coupling assisted transfer of magnetization not only for unraveling the overlap but also for the selective detection of enantiopure spectrum is reported. The experiment is simple, easy to implement and provides accurate eanantiomeric excess in addition to the determination of the proton-proton couplings of an enantiomer within a short experimental time (few minutes). (C) 2009 Elsevier Inc. All rights reserved.
Resumo:
The study deals with the breakup behavior of swirling liquid sheets discharging from gas-centered swirl coaxial atomizers with attention focused toward the understanding of the role of central gas jet on the liquid sheet breakup. Cold flow experiments on the liquid sheet breakup were carried out by employing custom fabricated gas-centered swirl coaxial atomizers using water and air as experimental fluids. Photographic techniques were employed to capture the flow behavior of liquid sheets at different flow conditions. Quantitative variation on the breakup length of the liquid sheet and spray width were obtained from the measurements deduced from the images of liquid sheets. The sheet breakup process is significantly influenced by the central air jet. It is observed that low inertia liquid sheets are more vulnerable to the presence of the central air jet and develop shorter breakup lengths at smaller values of the air jet Reynolds number Re-g. High inertia liquid sheets ignore the presence of the central air jet at smaller values of Re-g and eventually develop shorter breakup lengths at higher values of Re-g. The experimental evidences suggest that the central air jet causes corrugations on the liquid sheet surface, which may be promoting the production of thick liquid ligaments from the sheet surface. The level of surface corrugations on the liquid sheet increases with increasing Re-g. Qualitative analysis of experimental observations reveals that the entrainment process of air established between the inner surface of the liquid sheet and the central air jet is the primary trigger for the sheet breakup.
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Two new donor-acceptor type liquid crystalline semiconductors based on benzothiazole have been synthesized. Their structural, photophysical and electronic properties were investigated using X-ray diffraction, atomic force microscopy, cyclic voltammetry, UV-Vis, photoluminescence, and Raman spectroscopy. The liquid crystalline behaviour of the molecules was thoroughly examined by differential scanning calorimetry (DSC) and optical polarizing microscope. The DSC and thermogravimetric analysis (TGA) show that these materials posses excellent thermal stability and have decomposition temperatures in excess of 300 degrees C. Beyond 160 degrees C both molecules show a smectic A liquid crystalline phase that exists till about 240 degrees C. Field-effect transistors were fabricated by vacuum evaporating the semiconductor layer using standard bottom gate/top contact geometry. The devices exhibit p-channel behaviour with hole mobilities of 10(-2) cm(2)/Vs. (C) 2009 Elsevier B.V. All rights reserved.
Resumo:
We study the current produced in a Tomonaga-Luttinger liquid by an applied bias and by weak, pointlike impurity potentials which are oscillating in time. We use bosonization to perturbatively calculate the current up to second order in the impurity potentials. In the regime of small bias and low pumping frequency, both the dc and ac components of the current have power-law dependences on the bias and pumping frequencies with an exponent 2K-1 for spinless electrons, where K is the interaction parameter. For K < 1/2, the current grows large for special values of the bias. For noninteracting electrons with K=1, our results agree with those obtained using Floquet scattering theory for Dirac fermions. We also discuss the cases of extended impurities and of spin-1/2 electrons.