Liquid phase hydrogenation of aniline in a trickle bed reactor

A rate equation is developed for the liquid phase hydrogenation of aniline over cylindrical catalyst pellets of 30% nickel deposited on clay in a trickle bed reactor. The equation takes into account external and internal diffusional limitations, and describes the experimental data adequately. The hydrogenation reaction is first order with respect to hydrogen and zero order with respect to aniline. Effectiveness factors are in the range 0.003-0.03. Apparent activation energy of the reaction is 12.7 kcal/mol and true activation energy is 39.6 kcal/mol.

The problem of liquid droplet combustion-reexamination

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.

Critical behaviour of electrical resistivity in 5 binary liquid systems

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.

CO2-laser induced X-ray emission from high density gaseous targets

A theory for the emission of X-rays from a high density gaseous plasma interacting with CO2 laser is given. It predicts a sharp increase in the X-ray intensity for densities close to the critical.

Scaling for binary liquid systems and ferromagnets under pressure

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.

Theory of CO2-laser induced x-ray emission from high density gaseous targets

Abstract is not available.

Anomalous plasma heating by an intense laser beam

Heating of laser produced plasmas by an instability is investigated. For intense laser beams anomalous absorption is found. A comparison is made with the experiment.

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.

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.

Spinodal Decomposition in Tellurite-Based Glasses Induced by Excimer Laser Irradiation

Tellurite-based glasses in the TeO2-K3Li2Nb5O15, TeO2-Ba5Li2Ti2Nb8O30, and V2Te2O9 were fabricated by the conventional melt-quenching technique. Amorphous and glassy characteristics of the as-quenched samples were established via the X-ray powder diffraction technique and differential thermal analysis, respectively. The as-quenched samples were irradiated by an excimer laser (248 nm). The effect of laser power, duration of irradiation, and the frequency of the laser pulses on the surface features of the above glasses were studied. The optical microscopic studies carried out on the above systems revealed the presence of quasi-periodic and periodic structures on their surfaces. The local compositional variations of these structures were confirmed by back-scattered electron imaging using scanning electron microscope accompanied by energy-dispersive X-ray analysis. These results were convincing enough to state that the glasses in the present investigations had undergone spinodal decomposition on laser irradiation. The incidence of the interconnected texture of two different phases was observed owing to the quenching effect produced by the heating and cooling cycle of the successive laser pulses. Ring- and line-shaped patterns were also observed, respectively, when the pulse frequency of the laser and the duration of irradiation were increased.

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.