Diffusion hydrodynamic

This book provides the results of research into the development of scientific fundamentals, the technical design and industrial application of brand new technologies and devices for fast liquid-phase turbulent processes in the chemical, petrochemical, and petroleum industries. The macrokinetic approach, considering processes of diffusion, hydrodynamics, and heat transfer, has been developed and used for the advancement of fundamental knowledge and technologically important equations to enable the calculation of mass and heat transfer processes, which accompany fast chemical reactions and well-developed turbulence. This new family of chemical devices has been proposed for the intensification of fast liquid-phase processes through the creation of optimal hydrodynamic conditions for reacting media flows in a reaction zone. 

Auxiliary separation mechanisms — that depend on the size of macromolecules - and support the SEC separation (restricted) diffusion, hydrodynamic processes. 

Besides electrokinetic transport, chemical reactions also occur at the electrode surfaces (i.e., water electrolysis reactions with production of at the anode and OH at the cathode). Common mass-transport mechanisms like diffusion or convection and physical and chemical interactions of the species with the medium also occur. In a low-permeable porous medium under an electrical field, the major transport mechanism through the soil matrix during treatment for nonionic chemical species consists mainly of electro-osmosis, electrophoresis, molecular diffusion, hydrodynamic dispersion (molecular diffusion and dispersion varying with the heterogeneity of soils and fluid velocity [8]), sorption/ desorption, and chemical or biochemical reactions. Since related experiments are conducted in a relatively short period of time, the chemical and biochemical reactions that occur in the soil water are neglected [9]. 

The cleaning process proceeds by one of three primary mechanisms solubilization, emulsification, and roll-up [229]. In solubilization the oily phase partitions into surfactant micelles that desorb from the solid surface and diffuse into the bulk. As mentioned above, there is a body of theoretical work on solubilization [146, 147] and numerous experimental studies by a variety of spectroscopic techniques [143-145,230]. Emulsification involves the formation and removal of an emulsion at the oil-water interface the removal step may involve hydrodynamic as well as surface chemical forces. Emulsion formation is covered in Chapter XIV. In roll-up the surfactant reduces the contact angle of the liquid soil or the surface free energy of a solid particle aiding its detachment and subsequent removal by hydrodynamic forces. Adam and Stevenson s beautiful photographs illustrate roll-up of lanoline on wood fibers [231]. In order to achieve roll-up, one requires the surface free energies for soil detachment illustrated in Fig. XIII-14 to obey... 

Similarly to the response at hydrodynamic electrodes, linear and cyclic potential sweeps for simple electrode reactions will yield steady-state voltammograms with forward and reverse scans retracing one another, provided the scan rate is slow enough to maintain the steady state [28, 35, 36, 37 and 38]. The limiting current will be detemiined by the slowest step in the overall process, but if the kinetics are fast, then the current will be under diffusion control and hence obey the above equation for a disc. The slope of the wave in the absence of IR drop will, once again, depend on the degree of reversibility of the electrode process. 

In dilute solutions, tire dependence of tire diffusion coefficient on tire molecular weight is different from tliat found in melts, eitlier entangled or not. This difference is due to tire presence of hydrodynamic interactions among tire solvent molecules. Such interactions arise from tire necessity to transfer solvent molecules from tire front to tire back of a moving particle. The motion of tire solvent gives rise to a flow field which couples all molecules over a... 

The diffusion layer widtli is very much dependent on tire degree of agitation of tire electrolyte. Thus, via tire parameter 5, tire hydrodynamics of tire solution can be considered. Experimentally, defined hydrodynamic conditions are achieved by a rotating cylinder, disc or ring-disc electrodes, for which analytical solutions for tire diffusion equation are available [37, 4T, 42 and 43]. 

Thus one must rely on macroscopic theories and empirical adjustments for the determination of potentials of mean force. Such empirical adjustments use free energy data as solubilities, partition coefficients, virial coefficients, phase diagrams, etc., while the frictional terms are derived from diffusion coefficients and macroscopic theories for hydrodynamic interactions. In this whole field of enquiry progress is slow and much work (and thought ) will be needed in the future. 

External Fluid Film Resistance. A particle immersed ia a fluid is always surrounded by a laminar fluid film or boundary layer through which an adsorbiag or desorbiag molecule must diffuse. The thickness of this layer, and therefore the mass transfer resistance, depends on the hydrodynamic conditions. Mass transfer ia packed beds and other common contacting devices has been widely studied. The rate data are normally expressed ia terms of a simple linear rate expression of the form... 

Reviews of concentration polarization have been reported (14,38,39). Because solute wall concentration may not be experimentally measurable, models relating solute and solvent fluxes to hydrodynamic parameters are needed for system design. The Navier-Stokes diffusion—convection equation has been numerically solved to calculate wall concentration, and thus the water flux and permeate quaUty (40). 

Volt mmetiy. Diffusional effects, as embodied in equation 1, can be avoided by simply stirring the solution or rotating the electrode, eg, using the rotating disk electrode (RDE) at high rpm (3,7). The resultant concentration profiles then appear as shown in Figure 5. A time-independent Nernst diffusion layer having a thickness dictated by the laws of hydrodynamics is estabUshed. For the RDE,... 

Influence of Chemical Reactions on Uq and When a chemical reaction occurs, the transfer rate may be influenced by the chemical reac tion as well as by the purely physical processes of diffusion and convection within the two phases. Since this situation is common in gas absorption, gas absorption will be the focus of this discussion. One must consider the impacts of chemical equilibrium and reac tion kinetics on the absorption rate in addition to accounting for the effec ts of gas solubility, diffusivity, and system hydrodynamics. 

The other mechanism appears in scrubbers. When water vapor diffuses from a gas stream to a cold surface and condenses, there is a net hydrodynamic flow of the noncondensable gas directed toward the surface. This flow, termed the Stefan flow, carries aerosol particles to the condensing surface (Goldsmith and May, in Davies, Aero.sol Science, Academic, New York, 1966) and can substantially improve the performance of a scrubber. However, there is a corresponding Stefan flow directed away from a surface at which water is evaporating, and this will tend to repel aerosol particles from the surface. 

In what follows, both macromixing and micromixing models will be introduced and a compartmental mixing model, the segregated feed model (SFM), will be discussed in detail. It will be used in Chapter 8 to model the influence of the hydrodynamics on a meso- and microscale on continuous and semibatch precipitation where using CFD, diffusive and convective mixing parameters in the reactor are determined. 

These models are designed to reproduce the random movement of flexible polymer chains in a solvent or melt in a more or less realistic way. Simulational results which reproduce in simple cases the so-called Rouse [49] or Zimm [50] dynamics, depending on whether hydrodynamic interactions in the system are neglected or not, appear appropriate for studying diffusion, relaxation, and transport properties in general. In all dynamic models the monomers perform small displacements per unit time while the connectivity of the chains is preserved during the simulation. 

The scaling dependence of the diffusion coefficient on N and Cobs Iso poses a number of questions. While the original scaling predictions, based on reptation dynamics [26,38], oc N, have been verified by some measurements [91,98], significant discrepancies have been reported too [95,96]. Attempts to interpret existing data in terms of alternative models, e.g., by the so-called hydrodynamic scaling model [96], fail to describe observations [100,101]. 

Short-time Brownian motion was simulated and compared with experiments [108]. The structural evolution and dynamics [109] and the translational and bond-orientational order [110] were simulated with Brownian dynamics (BD) for dense binary colloidal mixtures. The short-time dynamics was investigated through the velocity autocorrelation function [111] and an algebraic decay of velocity fluctuation in a confined liquid was found [112]. Dissipative particle dynamics [113] is an attempt to bridge the gap between atomistic and mesoscopic simulation. Colloidal adsorption was simulated with BD [114]. The hydrodynamic forces, usually friction forces, are found to be able to enhance the self-diffusion of colloidal particles [115]. A novel MC approach to the dynamics of fluids was proposed in Ref. 116. Spinodal decomposition [117] in binary fluids was simulated. BD simulations for hard spherocylinders in the isotropic [118] and in the nematic phase [119] were done. A two-site Yukawa system [120] was studied with... 

Most theoretical studies of osmosis and reverse osmosis have been carried out using macroscopic continuum hydrodynamics [5,8-13]. The models used include those that treat the wall as either nonporous or porous. In the nonporous models the membrane surface is assumed homogeneous and nonporous. Transport occurs by the molecules dissolving in the membrane phase and then diffusing through the membrane. Mass transfer across the membrane in these models is usually described using the solution-diffusion... 

These apparent restrictions in size and length of simulation time of the fully quantum-mechanical methods or molecular-dynamics methods with continuous degrees of freedom in real space are the basic reason why the direct simulation of lattice models of the Ising type or of solid-on-solid type is still the most popular technique to simulate crystal growth processes. Consequently, a substantial part of this article will deal with scientific problems on those time and length scales which are simultaneously accessible by the experimental STM methods on one hand and by Monte Carlo lattice simulations on the other hand. Even these methods, however, are too microscopic to incorporate the boundary conditions from the laboratory set-up into the models in a reahstic way. Therefore one uses phenomenological models of the phase-field or sharp-interface type, and finally even finite-element methods, to treat the diffusion transport and hydrodynamic convections which control a reahstic crystal growth process from the melt on an industrial scale. 

We have so far assumed that the atoms deposited from the vapor phase or from dilute solution strike randomly and balHstically on the crystal surface. However, the material to be crystallized would normally be transported through another medium. Even if this is achieved by hydrodynamic convection, it must nevertheless overcome the last displacement for incorporation by a random diffusion process. Therefore, diffusion of material (as well as of heat) is the most important transport mechanism during crystal growth. An exception, to some extent, is molecular beam epitaxy (MBE) (see [3,12-14] and [15-19]) where the atoms may arrive non-thermalized at supersonic speeds on the crystal surface. But again, after their deposition, surface diffusion then comes into play. 

In many crystal growth phenomena, transportation of material occurs not only via diffusion but also via hydrodynamic convection. We assume... 

Here, D is the diffusion constant for heat or material and the kinematic viscosity of the liquid. A consequence of the existence of such a diffusive surface barrier is that the diffusion length = D/F is to be replaced by in all formulas, as soon as growth rate V the more important become the hydrodynamic convection effects. 

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