Critical Exponent β and Rectilinear Diameter of the Binary-Liquid System Carbon Disulfide + Nitromethane

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).

Rate Model and Mechanism of Liquid-Phase Oxidation of Propionaldehyde

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.

Adsorption and Unfolding of Lysozyme at a Polarized Aqueous-Organic Liquid Interface

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.

NMR spectra of 2-fluoropyridine in nematic liquid crystals

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.

Effects of mould filling on evolution of the solid-liquid interface during solidification

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.

Liquid-liquid critical phenomena. The coexistence curve of n-heptane-acetic anhydride

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.

Determination of skin friction in strong pressure-gradient equilibrium and near-equilibrium turbulent boundary layers

The conventional Clauser-chart method for determination of local skin friction in zero or weak pressure-gradient turbulent boundary layer flows fails entirely in strong pressure-gradient situations. This failure occurs due to the large departure of the mean velocity profile from the universal logarithmic law upon which the conventional Clauser-chart method is based. It is possible to extend this method,even for strong pressure-gradient situations involving equilibrium or near-equilibrium turbulent boundary layers by making use of the so-called non-universal logarithmic laws. These non-universal log laws depend on the local strength of the pressure gradient and may be regarded as perturbations of the universal log law.The present paper shows that the modified Clauser-chart method, so developed, yields quit satisfactory results in terms of estimation of local skin friction in strongly accelerated or retarded equilibrium and near-equilibrium turbulent boundary layers that are not very close to relaminarization or separation.

CFD analysis of high frequency miniature pulse tube refrigerators for space applications with thermal non-equilibrium model

High frequency, miniature, pulse tube cryocoolers are extensively used in space applications because of their simplicity. Parametric studies of inertance type pulse tube cooler are performed with different length-to-diameter ratios of the pulse tube with the help of the FLUENT (R) package. The local thermal non-equilibrium of the gas and the matrix is taken into account for the modeling of porous zones, in addition to the wall thickness of the components. Dynamic characteristics and the actual mechanism of energy transfer in pulse are examined with the help of the pulse tube wall time constant. The heat interaction between pulse tube wall and the oscillating gas, leading to surface heat pumping, is quantified. The axial heat conduction is found to reduce the performance of the pulse tube refrigerator. The thermal non-equilibrium predicts a higher cold heat exchanger temperature compared to thermal equilibrium. The pressure drop through the porous medium has a strong non-linear effect due to the dominating influence of Forchheimer term over that of the linear Darcy term at high operating frequencies. The phase angle relationships among the pressure, temperature and the mass flow rate in the porous zones are also important in determining the performance of pulse tuberefrigerator.

Vitrification, relaxation and free volume in glycerol-water binary liquid mixture:Spin probe ESR studies

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.

Selective detection of single-enantiomer spectrum of chiral molecules aligned in the polypeptide liquid crystalline solvent: Transition selective one-dimensional H-1-H-1 COSY

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.

Liquid Sheet Breakup in Gas-Centered Swirl Coaxial Atomizers

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.

Synthesis of liquid crystalline benzothiazole base derivatives: A study of their optical and electrical properties

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.

Charge transport in a Tomonaga-Luttinger liquid: Effects of pumping and bias

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.

Multiphase porous media model for Intermittent Microwave Convective Drying (IMCD) of food

Intermittent microwave convective (IMCD) drying is an advanced drying technology that improves both energy efficiency and food quality during the drying of food materials. Despite numerous experimental studies available for IMCD, there is no complete multiphase porous media model available to describe the process. A multiphase porous media model considering liquid water, gases and the solid matrix inside the food during drying can provide in depth understanding of IMCD. In this article, firstly a multiphase porous media model was developed for IMCD. Then the model is validated against experimental data by comparing moisture content and temperature distributions after each heating and tempering periods. The profile of vapour pressures and evaporation during IMCD are presented and discussed. The relative contribution of water and vapour fluxes due to gas pressure and diffusion demonstrated that the fluxes due are relatively higher in IMCD compared to convection drying and this makes the IMCD faster.