Molecular diffusion particle

There is an intimate connection at the molecular level between diffusion and random flight statistics. The diffusing particle, after all, is displaced by random collisions with the surrounding solvent molecules, travels a short distance, experiences another collision which changes its direction, and so on. Such a zigzagged path is called Brownian motion when observed microscopically, describes diffusion when considered in terms of net displacement, and defines a three-dimensional random walk in statistical language. Accordingly, we propose to describe the net displacement of the solute in, say, the x direction as the result of a r -step random walk, in which the number of steps is directly proportional to time ... 

Neglecting flow nonuniformities, the contributions of molecular diffusion and turbulent mixing arising from stream sphtting and recombination around the sorbent particles can be considered additive [Langer et al., Int. ]. Heat and Mass Transfer, 21, 751 (1978)] thus, the axial dispersion coefficient is given by ... 

An important mixing operation involves bringing different molecular species together to obtain a chemical reaction. The components may be miscible liquids, immiscible liquids, solid particles and a liquid, a gas and a liquid, a gas and solid particles, or two gases. In some cases, temperature differences exist between an equipment surface and the bulk fluid, or between the suspended particles and the continuous phase fluid. The same mechanisms that enhance mass transfer by reducing the film thickness are used to promote heat transfer by increasing the temperature gradient in the film. These mechanisms are bulk flow, eddy diffusion, and molecular diffusion. The performance of equipment in which heat transfer occurs is expressed in terms of forced convective heat transfer coefficients. 

The mass transfer effect is relevant when the chemical reaction is far faster than the molecular diffusion, i.e. Ha > 1. The rapid formation of precipitate particles should then occur spatially distributed. The relative rate of particle formation to chemical reaction and/or diffusion can as yet be evaluated only via lengthy calculations. 

Hydrodynamic Dispersion Macroscopic dispersion is produced in a capillar) even in tlie absence of molecular diffusion because of the velocity profile produced by the adherence of the fluid to tlie wall. Tlris causes fluid particles at different radial positions to move relative to one anotlier, witli tlie result tliat a series of mixing-cup samples at tlie end of tlie capillary e.xhibits dispersion. 

Glaser and Litt (G4) have proposed, in an extension of the above study, a model for gas-liquid flow through a b d of porous particles. The bed is assumed to consist of two basic structures which influence the fluid flow patterns (1) Void channels external to the packing, with which are associated dead-ended pockets that can hold stagnant pools of liquid and (2) pore channels and pockets, i.e., continuous and dead-ended pockets in the interior of the particles. On this basis, a theoretical model of liquid-phase dispersion in mixed-phase flow is developed. The model uses three bed parameters for the description of axial dispersion (1) Dispersion due to the mixing of streams from various channels of different residence times (2) dispersion from axial diffusion in the void channels and (3) dispersion from diffusion into the pores. The model is not applicable to turbulent flow nor to such low flow rates that molecular diffusion is comparable to Taylor diffusion. The latter region is unlikely to be of practical interest. The model predicts that the reciprocal Peclet number should be directly proportional to nominal liquid velocity, a prediction that has been confirmed by a few determinations of residence-time distribution for a wax desulfurization pilot reactor of 1-in. diameter packed with 10-14 mesh particles. 

Explain why, when applying the equation to reaction in a porous catalyst particle, it is necessary to replace the molecular diffusivity D by an effective diffusivity De. 

Mass transfer in a gas-liquid or a liquid-liquid reactor is mainly determined by the size of the fluid particles and the interfacial area. The diffusivity in gas phase is high, and usually no concentration gradients are observed in a bubble, whereas large concentration gradients are observed in drops. An internal circulation enhances the mass transfer in a drop, but it is still the molecular diffusion in the drop that limits the mass transfer. An estimation, from the time constant, of the time it wiU take to empty a 5-mm drop is given by Td = d /4D = (10 ) /4 x 10 = 6000s. The diffusion timescale varies with the square of the diameter of the drop, so... 

Most descriptions of the dynamics of molecular or particle motion in solution require a knowledge of the frictional properties of the system. This is especially true for polymer solutions, colloidal suspensions, molecular transport processes, and biomolecular conformational changes. Particle friction also plays an important role in the calculation of diffusion-influenced reaction rates, which will be discussed later. Solvent multiparticle collision dynamics, in conjunction with molecular dynamics of solute particles, provides a means to study such systems. In this section we show how the frictional properties and hydrodynamic interactions among solute or colloidal particles can be studied using hybrid MPC-MD schemes. 

Molecular diffusion and/or Knudsen flow of reactants from the exterior surface of the catalyst particle into the interior pore structure. 

Dispersion in packed tubes with wall effects was part of the CFD study by Magnico (2003), for N — 5.96 and N — 7.8, so the author was able to focus on mass transfer mechanisms near the tube wall. After establishing a steady-state flow, a Lagrangian approach was used in which particles were followed along the trajectories, with molecular diffusion suppressed, to single out the connection between flow and radial mass transport. The results showed the ratio of longitudinal to transverse dispersion coefficients to be smaller than in the literature, which may have been connected to the wall effects. The flow structure near the wall was probed by the tracer technique, and it was observed that there was a boundary layer near the wall of width about Jp/4 (at Ret — 7) in which there was no radial velocity component, so that mass transfer across the layer... 

From a molecular point of view inside a catalyst particle, diffusion may be considered to occur by three different modes molecular, Knudsen, and surface. Molecular diffusion is the result of molecular encounters (collisions) in the void space (pores) of the particle. Knudsen diffusion is the result of molecular collisions with the walls of the pores. Molecular diffusion tends to dominate in relatively large pores at high P, and Knudsen diffusion tends to dominate in small pores at low P. Surface diffusion results from the migration of adsorbed species along the surface of the pore because of a gradient in surface concentration. 

The effective diffusivity De is a characteristic of the particle that must be measured for greatest accuracy. However, in the absence of experimental data, De may be estimated in terms of molecular diffusivity, Dab (for diffusion of A in the binary system A + B), Knudsen diffusivity, DK, particle voidage, p, and a measure of the pore structure called the particle tortuosity, Tp. 

For a free-falling spherical particle of radius R moving with velocity u relative to a fluid of density p and viscosity p, and in which the molecular diffusion coefficient (for species A) is DA, the Ranz-Marshall correlation relates the Sherwood number (Sh), which incorporates kAg, to the Schmidt number (Sc) and the Reynolds number (Re) ... 

The Schmidt number is the ratio of kinematic viscosity to molecular diffusivity. Considering liquids in general and dissolution media in particular, the values for the kinematic viscosity usually exceed those for diffusion coefficients by a factor of 103 to 104. Thus, Prandtl or Schmidt numbers of about 103 are usually obtained. Subsequently, and in contrast to the classical concept of the boundary layer, Re numbers of magnitude of about Re > 0.01 are sufficient to generate Peclet numbers greater than 1 and to justify the hydrodynamic boundary layer concept for particle-liquid dissolution systems (Re Pr = Pe). It can be shown that [(9), term 10.15, nomenclature adapted]... 

Since the absolute thickness of the effective hydrodynamic boundary layer is very small, below a particular size range minimum, no hydrodynamic effects are perceived experimentally with varying agitation. This, however, does not mean, that there are no such influences Further, the mechanisms of mass transfer and dissolution may change for very small particles depending on a number of factors, such as the fluid viscosity, the Sherwood number (the ratio of mass diffusivity to molecular diffusivity), and the power input per unit mass of fluid. 

There is apparently an inherent anomaly in the heat and mass transfer results in that, at low Reynolds numbers, the Nusselt and Sherwood numbers (Figures. 6.30 and 6.27) are very low, and substantially below the theoretical minimum value of 2 for transfer by thermal conduction or molecular diffusion to a spherical particle when the driving force is spread over an infinite distance (Volume 1, Chapter 9). The most probable explanation is that at low Reynolds numbers there is appreciable back-mixing of gas associated with the circulation of the solids. If this is represented as a diffusional type of process with a longitudinal diffusivity of DL, the basic equation for the heat transfer process is ... 

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