Size methods Smoluchowski theory

At the simplest level, the rate of flow-induced aggregation of compact spherical particles is described by Smoluchowski s theory [Eq. (32)]. Such expressions may then be incorporated into population balance equations to determine the evolution of the agglomerate size distribution with time. However with increase in agglomerate size, complex (fractal) structures may be generated that preclude analysis by simple methods as above. 

There is a close parallel between this development and the microscopic theory of condensed-phase chemical reactions. First, the questions one asks are very nearly the same. In Section III we summarized several configuration space approaches to this problem. These methods assume the validity of a diffusion or Smoluchowski equation, which is based on a continuum description of the solvent. Such theories will surely fail at the close encounter distance required for reaction to take place. In most situations of chemical interest, the solute and solvent molecules are comparable in size and the continuum description no longer applies. Yet we know that these simple approaches are often quite successful, even when applied to the small molecule case. Thus we again have a microscopic relaxation process exhibiting a strong hydrodynamic component. This hydrodynamic component again gives rise to a power law decay in the rate kernel (cf. 

In order to apply the Smoluchowski equation (Equations (1.3), (2.1), (3.29)), we need values for the least distance of approach (rAn) and the diffusion coefficient (Dab)- The value of tab can be estimated from molecular volumes (Section 2.5.1.2). The diffusion coefficient can be determined by various methods, but experimental values are available only for a minority of the myriad possible situations. A common practice is to use the Stokes-Einstein relation (Section 1.2.3), which rests on the assumption that solute molecules in motion behave like macroscopic particles to which classical hydrodynamic theory can be applied. We shall first outline (a) the relation between the diffusion coefficient D and the mechanics of motion of particles in fluids, leading to the Stokes-Einstein equation relating D to solute size and solvent viscosity and (b) the direct experimental determination of D. We shall then (c) compare the results and note the reservations that are required in relying on the Stokes-Einstein estimates of D in various cases. 

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