Coagulation Smoluchowski theory

The coagulation, flocculation, and adsorption processes were modeled mathematically using classical coagulation theory as a starting point. The Smoluchowski equation for orthokinetic coagulation in laminar flow is written (18)... 

Various analytical solutions to the von Smoluchowski equation set have been developed over the years, originating with the solution presented by von Smoluchowski coinciding with the expression of coagulation theory in 1917 [1]. No general analytical solutions to the von Smoluchowski equation are available, but many expressions have been developed with simplifying assumptions. This section will review the available analytical solutions and discuss the uses and limitations of the solutions. 

For a more complete understanding of colloid stability, we need to address the kinetics of aggregation. The theory discussed here was developed to describe coagulation of charged colloids, but it does apply to other cases as well. First, we consider the case of so-called rapid coagulation, which means that two particles will aggregate as soon as they meet (at high salt concentration, for instance). This was considered by von Smoluchowski 1561 here we follow [39, 57]. 

There are two general theories of the stabUity of lyophobic coUoids, or, more precisely, two general mechanisms controlling the dispersion and flocculation of these coUoids. Both theories regard adsorption of dissolved species as a key process in stabilization. However, one theory is based on a consideration of ionic forces near the interface, whereas the other is based on steric forces. The two theories complement each other and are in no sense contradictory. In some systems, one mechanism may be predominant, and in others both mechanisms may operate simultaneously. The fundamental kinetic considerations common to both theories are based on Smoluchowski s classical theory of the coagulation of coUoids. 

Smoluchowski, M.V., 1917. Mathematical theory of the kinetics of coagulation of colloidal systems. Zeitschrift fur Physikalische Chemie, 92, 129-168. 

All models described up to here belong to the class of equilibrium theories. They have the advantage of providing structural information on the material during the liquid-solid transition. Kinetic theories based on Smoluchowski s coagulation equation [45] have recently been applied more and more to describe the kinetics of gelation. The Smoluchowski equation describes the time evolution of the cluster size distribution N(k) ... 

The original theory of diffusional coagulation of spherical aerosol particles was developed by von Smoluchowski (1916,1917). The underlying hypothesis in this theory is that every aerosol particle acts as a sink for the diffusing species. The concentration of the diffusing species at the surface of the aerosol particle is assumed to be zero. At some distance away, the concentration is the bulk concentration. 

Studies on orthokinetic flocculation (shear flow dominating over Brownian motion) show a more ambiguous picture. Both rate increases (9,10) and decreases (11,12) compared with orthokinetic coagulation have been observed. Gregory (12) treated polymer adsorption as a collision process and used Smoluchowski theory to predict that the adsorption step may become rate limiting in orthokinetic flocculation. Qualitative evidence to this effect was found for flocculation of polystyrene latex, particle diameter 1.68 pm, in laminar tube flow. Furthermore, pretreatment of half of the latex with polymer resulted in collision efficiencies that were more than twice as high as for coagulation. 

Smoluchowski, who worked on the rate of coagulation of colloidal particles, was a pioneer in the development of the theory of diffusion-controlled reactions. His theory is based on the assumption that the probability of reaction is equal to 1 when A and B are at the distance of closest approach (Rc) ( absorbing boundary condition ), which corresponds to an infinite value of the intrinsic rate constant kR. The rate constant k for the dissociation of the encounter pair can thus be ignored. As a result of this boundary condition, the concentration of B is equal to zero on the surface of a sphere of radius Rc, and consequently, there is a concentration gradient of B. The rate constant for reaction k (t) can be obtained from the flux of B, in the concentration gradient, through the surface of contact with A. This flux depends on the radial distribution function of B, p(r, t), which is a solution of Fick s equation... 

What is meant by rapid coagulation What is the basic principle behind the Smoluchowski theory of rapid coagulation What is the rate coefficient for rapid coagulation How is it defined, and what properties of the dispersion determine its magnitude What are the limitations of this theory as presented in the text ... 

Kinetics is concerned with many-particle systems which require movements in space and time of individual particles. The first observations on the kinetic effect of individual molecular movements were reported by R. Brown in 1828. He observed the outward manifestation of molecular motion, now referred to as Brownian motion. The corresponding theory was first proposed in a satisfactory form in 1905 by A. Einstein. At the same time, the Polish physicist and physical chemist M. v. Smolu-chowski worked on problems of diffusion, Brownian motion (and coagulation of colloid particles) [M. v. Smoluchowski (1916)]. He is praised by later leaders in this field [S. Chandrasekhar (1943)] as a scientist whose theory of density fluctuations represents one of the most outstanding achievements in molecular physical chemistry. Further important contributions are due to Fokker, Planck, Burger, Furth, Ornstein, Uhlenbeck, Chandrasekhar, Kramers, among others. An extensive list of references can be found in [G.E. Uhlenbeck, L.S. Ornstein (1930) M.C. Wang, G.E. Uhlenbeck (1945)]. A survey of the field is found in [N. Wax, ed. (1954)]. 

The simplest class of bimolecular reactions involves only one type of mobile particles A and could result either in particle coagulation (coalescence, fusion) A + A —> A, or annihilation, A + A — 0 (inert product). Their simplicity in conjunction with the simple topology of d = 1 allows us to solve the problem exactly, which makes it very attractive for testing different approximations and computer simulations. In the standard chemical kinetics (i.e., mean-field theory, Section 2.1.1) we expect in d = 2 and 3 for both reactions mentioned trivial behaviour quite similar to the A+B — 0 reaction, i.e., tia( ) oc t-1, as t — oo. For d = 1 in terms of the Smoluchowski theory the joint density obeys respectively the equation (4.1.56) with V2 = and D = 2Da. 

The theory of coagulation was developed by von Smoluchowski (1917) and found to be correct as long as particles are not attracted or repulsed by electric charges, or go into solution. Von Smoluchowski s... 

This result was first obtained by Smoluchowski. This analysis does not take into account local flows accompanying the draining of fluid from the region between the approaching particles or particle motion normal to the main flow direction. These flows would change the simple shear field assumed in the analysis and probably reduce the cross section below the result of the geometric theory. However, experimental results such as those reponed below lend support to the approximate analysis. This subject is discussed further in the section on turbulent coagulation. 

In the approach adopted in my first edition, the derivation and use of the general dynamic equation for the particle size distribution played a central role. This special form of a population balance equation incorporated the Smoluchowski theory of coagulation and gas-to-panicle conversion through a Liouville term with a set of special growth laws coagulation and gas-to-particle conversion are processes that take place within an elemental gas volume. Brownian diffusion and external force fields transport particles across the boundaries of the elemental volume. A major limitation on the formulation was the assumption that the panicles were liquid droplets that coalesced instantaneously after collision. 

The kinetic theory of fast irreversible coagulation was developed by von Smoluchowski. Later the theory was extended to the case of slow and reversible coagulation. In any case of coagulation (flocculation), the general set of kinetic equations reads... 

A quantitative expression for the rate of coalescence of droplets in a macroemulsion, which includes most of the factors discussed previously, was developed by Davies and Rideal (1963), based on the von Smoluchowski (1916) theory of the coagulation of colloids. 

There exists an extensive literature on the theory of coagulation (Fuchs, 1964 Zebel, 1966 Hidy and Brock, 1970 Twomey, 1977), and we can treat here only the most salient features. In the absence of external forces, the aerosol particles undergo collisions with each other due to their thermal (Brownian) motion. The mathematical description of thermal coagulation goes back to the classical work of Smoluchowski (1918) on hydrosols. Application to aerosols seems to have been made first by Whitlaw-Gray and Patterson (1932). Let dN, = f(r,) dr, and dN2=f(r2) dr2 describe the number densities of particles in the size intervals r, + dr, and r2+dr2,... 

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