Organic reactions in supercritical fluids: Continuous, selective and green

Supercritical fluids (SCFs) offer a wide range of opportunities as media for chemical reactions and supercritical CO2, ScCO2, is becoming increasingly important as a benign replacement for more toxic solvents.1 High pressure reactions, however, are more capital intensive than conventional low pressure processes. Therefore, supercritical fluids will only gain widespread acceptance in those areas where the fluids give real chemical advantages as well as environmental benefits. This lecture gives a brief account of the use of flow reactors for continuous reactions in supercritical fluids, particularly those of interest for the manufacture of fine chemicals.

Probe for Measurements of Density/Conductivity in Flows of Conducting Fluids

A probe utilizing the bipolar pulse method to measure the density of a conducting fluid has been developed. The probe is specially designed such that the concentration of a stream tube can be sampled continuously. The density was determined indirectly from the measurement of solution conductivity. The probe was calibrated using standard NaCl solutions of varying molarity and was able to rapidly determine the density of a fluid with continuously varying conductance. Measurements of the conductivity profiles, corresponding density profiles, and their fluctuation levels are demonstrated in a channel flow with an electrolyte injected from a slot in one wall.

Rossby Waves With Linear Topography In Barotropic Fluids

Rossby waves are the most important waves in the atmosphere and ocean, and are parts of a large-scale system in fluid. The theory and observation show that, they satisfy quasi-geostrophic and quasi-static equilibrium approximations. In this paper, solitary Rossby waves induced by linear topography in barotropic fluids with a shear flow are studied. In order to simplify the problem, the topography is taken as a linear function of latitude variable y, then employing a weakly nonlinear method and a perturbation method, a KdV (Korteweg-de Vries) equation describing evolution of the amplitude of solitary Rossby waves induced by linear topography is derived. The results show that the variation of linear topography can induce the solitary Rossby waves in barotropic fluids with a shear flow, and extend the classical geophysical theory of fluid dynamics.

Vertically forced surface wave in weakly viscous fluids bounded in a circular cylindrical vessel

Two-time scale perturbation expansions were developed in weakly viscous fluids to investigate surface wave motions by linearizing the Navier-Stokes equation in a circular cylindrical vessel which is subject to a vertical oscillation. The fluid field was divided into an outer potential flow region and an inner boundary layer region. A linear amplitude equation of slowly varying complex amplitude, which incorporates a damping term and external excitation, was derived for the weakly viscid fluids. The condition for the appearance of stable surface waves was obtained and the critical curve was determined. In addition, an analytical expression for the damping coefficient was determined and the relationship between damping and other related parameters (such as viscosity, forced amplitude, forced frequency and the depth of fluid, etc.) was presented. Finally, the influence both of the surface tension and the weak viscosity on the mode formation was described by comparing theoretical and experimental results. The results show that when the forcing frequency is low, the viscosity of the fluid is prominent for the mode selection. However, when the forcing frequency is high, the surface tension of the fluid is prominent.

Proper orthogonal decomposition of oscillatory Marangoni flow in half-zone liquid bridges of low-Pr fluids

Proper orthogonal decomposition (POD) using method of snapshots was performed on three different types of oscillatory Marangoni flows in half-zone liquid bridges of low-Pr fluid (Pr = 0.01). For each oscillation type, a series of characteristic modes (eigenfunctions) have been extracted from the velocity and temperature disturbances, and the POD provided spatial structures of the eigenfunctions, their oscillation frequencies, amplitudes, and phase shifts between them. The present analyses revealed the common features of the characteristic modes for different oscillation modes: four major velocity eigenfunctions captured more than 99% of the velocity fluctuation energy form two pairs, one of which is the most energetic. Different from the velocity disturbance, one of the major temperature eigenfunctions makes the dominant contribution to the temperature fluctuation energy. On the other hand, within the most energetic velocity eigenfuction pair, the two eigenfunctions have similar spatial structures and were tightly coupled to oscillate with the same frequency, and it was determined that the spatial structures and phase shifts of the eigenfunctions produced the different oscillatory disturbances. The interaction of other major modes only enriches the secondary spatio-temporal structures of the oscillatory disturbances. Moreover, the present analyses imply that the oscillatory disturbance, which is hydrodynamic in nature, primarily originates from the interior of the liquid bridge. (C) 2007 Elsevier B.V. All rights reserved.

Numerical simulation of a single fluid particle rising in non-Newtonian fluids

In this work, a level set method is developed for simulating the motion of a fluid particle rising in non-Newtonian fluids described by generalized Newtonian as well as viscoelastic model fluids. As the shear-thinning model we use a Carreau-Yasuda model, and the viscoelastic effect can be modeled with Oldroyd-B constitutive equations. The control volume formulation with the SIMPLEC algorithm incorporated is used to solve the governing equations on a staggered Eulerian grid. The level set method is implemented to compute the motion of a bubble in a Newtonian fluid as one of typical examples for validation, and the computational results are in good agreement with the reported experimental data．The level set method is also applied for simulating a Newtonian drop rising in Carreau-Yasuda and Oldroyd-B fluids．Numerical results including noticeably negative wake behind the drop and viscosity field are obtained, and compare satisfactorily with the known literature data.

Investigation on average void fraction for air/non-Newtonian power-law fluids two-phase flow in downward inclined pipes

The present work has been carried out to investigate on the average void fraction of gas/non-Newtonian fluids flow in downward inclined pipes. The influences of pipe inclination angle on the average void fraction were studied experimentally. A simple correlation, which incorporated the method of Vlachos et al. for gas/Newtonain fluid horizontal flow, the correction factor of Farooqi and Richardson and the pipe inclination angle, was proposed to predict the average void fraction of gas/non-Newtonian power-law stratified flow in downward inclined pipes. The correlation was based on 470 data points covering a wide range of flow rates for different systems at diverse angles. A good agreement was obtained between theory and data and the fitting results could describe the majority of the experimental data within ±20%.

Kinetic theory of normal quantum fluids

Close to equilibrium, a normal Bose or Fermi fluid can be described by an exact kinetic equation whose kernel is nonlocal in space and time. The general expression derived for the kernel is evaluated to second order in the interparticle potential. The result is a wavevector- and frequency-dependent generalization of the linear Uehling-Uhlenbeck kernel with the Born approximation cross section.

The theory is formulated in terms of second-quantized phase space operators whose equilibrium averages are the n-particle Wigner distribution functions. Convenient expressions for the commutators and anticommutators of the phase space operators are obtained. The two-particle equilibrium distribution function is analyzed in terms of momentum-dependent quantum generalizations of the classical pair distribution function h(k) and direct correlation function c(k). The kinetic equation is presented as the equation of motion of a two -particle correlation function, the phase space density-density anticommutator, and is derived by a formal closure of the quantum BBGKY hierarchy. An alternative derivation using a projection operator is also given. It is shown that the method used for approximating the kernel by a second order expansion preserves all the sum rules to the same order, and that the second-order kernel satisfies the appropriate positivity and symmetry conditions.

Full and Model-Reduced Structure-Preserving Simulation of Incompressible Fluids

This thesis outlines the construction of several types of structured integrators for incompressible fluids. We first present a vorticity integrator, which is the Hamiltonian counterpart of the existing Lagrangian-based fluid integrator. We next present a model-reduced variational Eulerian integrator for incompressible fluids, which combines the efficiency gains of dimension reduction, the qualitative robustness to coarse spatial and temporal resolutions of geometric integrators, and the simplicity of homogenized boundary conditions on regular grids to deal with arbitrarily-shaped domains with sub-grid accuracy.

Both these numerical methods involve approximating the Lie group of volume-preserving diffeomorphisms by a finite-dimensional Lie-group and then restricting the resulting variational principle by means of a non-holonomic constraint. Advantages and limitations of this discretization method will be outlined. It will be seen that these derivation techniques are unable to yield symplectic integrators, but that energy conservation is easily obtained, as is a discretized version of Kelvin's circulation theorem.

Finally, we outline the basis of a spectral discrete exterior calculus, which may be a useful element in producing structured numerical methods for fluids in the future.

A molecular dynamics study of the microscopic properties of simple dense fluids

The microscopic properties of a two-dimensional model dense fluid of Lennard-Jones disks have been studied using the so-called "molecular dynamics" method. Analyses of the computer-generated simulation data in terms of "conventional" thermodynamic and distribution functions verify the physical validity of the model and the simulation technique.

The radial distribution functions g(r) computed from the simulation data exhibit several subsidiary features rather similar to those appearing in some of the g(r) functions obtained by X-ray and thermal neutron diffraction measurements on real simple liquids. In the case of the model fluid, these "anomalous" features are thought to reflect the existence of two or more alternative configurations for local ordering.

Graphical display techniques have been used extensively to provide some intuitive insight into the various microscopic phenomena occurring in the model. For example, "snapshots" of the instantaneous system configurations for different times show that the "excess" area allotted to the fluid is collected into relatively large, irregular, and surprisingly persistent "holes". Plots of the particle trajectories over intervals of 2.0 to 6.0 x 10^-12 sec indicate that the mechanism for diffusion in the dense model fluid is "cooperative" in nature, and that extensive diffusive migration is generally restricted to groups of particles in the vicinity of a hole.

A quantitative analysis of diffusion in the model fluid shows that the cooperative mechanism is not inconsistent with the statistical predictions of existing theories of singlet, or self-diffusion in liquids. The relative diffusion of proximate particles is, however, found to be retarded by short-range dynamic correlations associated with the cooperative mechanism--a result of some importance from the standpoint of bimolecular reaction kinetics in solution.

A new, semi-empirical treatment for relative diffusion in liquids is developed, and is shown to reproduce the relative diffusion phenomena observed in the model fluid quite accurately. When incorporated into the standard Smoluchowski theory of diffusion-controlled reaction kinetics, the more exact treatment of relative diffusion is found to lower the predicted rate of reaction appreciably.

Finally, an entirely new approach to an understanding of the liquid state is suggested. Our experience in dealing with the simulation data--and especially, graphical displays of the simulation data--has led us to conclude that many of the more frustrating scientific problems involving the liquid state would be simplified considerably, were it possible to describe the microscopic structures characteristic of liquids in a concise and precise manner. To this end, we propose that the development of a formal language of partially-ordered structures be investigated.

The instability of fluids with time dependent heating

The stability of a fluid having a non-uniform temperature stratification is examined analytically for the response of infinitesimal disturbances. The growth rates of disturbances have been established for a semi-infinite fluid for Rayleigh numbers of 10³, 10⁴, and 10⁵ and for Prandtl numbers of 7.0 and 0.7.

The critical Rayleigh number for a semi-infinite fluid, based on the effective fluid depth, is found to be 32, while it is shown that for a finite fluid layer the critical Rayleigh number depends on the rate of heating. The minimum critical Rayleigh number, based on the depth of a fluid layer, is found to be 1340.

The stability of a finite fluid layer is examined for two special forms of heating. The first is constant flux heating, while in the second, the temperature of the lower surface is increased uniformly in time. In both cases, it is shown that for moderate rates of heating the critical Rayleigh number is reduced, over the value for very slow heating, while for very rapid heating the critical Rayleigh number is greatly increased. These results agree with published experimental observations.

The question of steady, non-cellular convection is given qualitative consideration. It is concluded that, although the motion may originate from infinitesimal disturbances during non-uniform heating, the final flow field is intrinsically non-linear.