Smoluchowski number

Figure 25.4 Smoluchowski number (Sn latex polymer volume fraction (0p).

The flocculation rate is deterrnined from the Smoluchowski rate law which states that the rate is proportional to the square of the particle concentration by number inversely proportional to the fluid viscosity, and independent of particle size. 

As the particles in a coUoidal dispersion diffuse, they coUide with one another. In the simplest case, every coUision between two particles results in the formation of one agglomerated particle,ie, there is no energy barrier to agglomeration. Applying Smoluchowski s theory to this system, the half-life, ie, the time for the number of particles to become halved, is expressed as foUows, where Tj is the viscosity of the medium, k Boltzmann s constant T temperature and A/q is the initial number of particles. 

For applications in the field of micro reaction engineering, the conclusion may be drawn that the Navier-Stokes equation and other continuum models are valid in many cases, as Knudsen numbers greater than 10 are rarely obtained. However, it might be necessary to use slip boimdaty conditions. The first theoretical investigations on slip flow of gases were carried out in the 19th century by Maxwell and von Smoluchowski. The basic concept relies on a so-called slip length L, which relates the local shear strain to the relative flow velocity at the wall ... 

The collision frequency between drops may be estimated by means of Smoluchowski s theory (see, for example, Levich, 1962). The collision frequency (w = number of collisions per unit time per unit volume) for randomly distributed rigid equal-size spheres, occupying a volume fraction , is given by... 

In filtration, the particle-collector interaction is taken as the sum of the London-van der Waals and double layer interactions, i.e. the Deijagin-Landau-Verwey-Overbeek (DLVO) theory. In most cases, the London-van der Waals force is attractive. The double layer interaction, on the other hand, may be repulsive or attractive depending on whether the surface of the particle and the collector bear like or opposite charges. The range and distance dependence is also different. The DLVO theory was later extended with contributions from the Born repulsion, hydration (structural) forces, hydrophobic interactions and steric hindrance originating from adsorbed macromolecules or polymers. Because no analytical solutions exist for the full convective diffusion equation, a number of approximations were devised (e.g., Smoluchowski-Levich approximation, and the surface force boundary layer approximation) to solve the equations in an approximate way, using analytical methods. 

For example, in the case of PS and applying the Smoluchowski equation [333], it is possible to estimate the precipitation time, fpr, of globules of radius R and translation diffusion coefficient D in solutions of polymer concentration cp (the number of chains per unit volume) [334]. Assuming a standard diffusion-limited aggregation process, two globules merge every time they collide in the course of Brownian motion. Thus, one can write Eq. 2 ... 

If Po be the number of primary particles originally present in the sol and after a time t there be Pj, Pa, P3 primary, secondary and tertiary particles present v. Smoluchowski showed that... 

The Peclet number compares the effect of imposed shear (known as the convective effect) with the effect of diffusion of the particles. The imposed shear has the effect of altering the local distribution of the particles, whereas the diffusion (or Brownian motion) of the particles tries to restore the equilibrium structure. In a quiescent colloidal dispersion the particles move continuously in a random manner due to Brownian motion. The thermal motion establishes an equilibrium statistical distribution that depends on the volume fraction and interparticle potentials. Using the Einstein-Smoluchowski relation for the time scale of the motion, with the Stokes-Einstein equation for the diffusion coefficient, one can write the time taken for a particle to diffuse a distance equal to its radius R, as... 

As mentioned above, in 1917 M. Smoluchowski applied the theory of diffusion to this situation to evaluate the rate of doublet formation. According to Fick s first law (Equation (2.22)) J, the number of particles crossing a unit area toward the reference particle per unit of time is given by... 

The Peclet Number can be interpreted as the ratio between the transport time over the distance L by diffusion and by advection, respectively. Transport time by diffusion is expressed by the relation of Einstein and Smoluchowski (Eq. 18-8) ... 

Over molecular length scales, the diffusion distances become very short (< 1 nm) so that only very rapid events can be influenced by these short diffusion times. Necessarily, this limits the number of systems to only relatively few, where the rate at which the reactants can approach one another is slow or comparable with the rate at which the reactants react chemically with each other. Some typical systems which have been studied are discussed in Sect. 2. The Smoluchowski [3] theory of reactions in solution, which occur at a rate limited solely by how fast the reactants can approach each other (sufficiently closely to react chemically almost instantaneously) is discussed in Sect. 3. If the chemical reaction is not so rapid, the observed rate of reaction may be influenced by both the rate of approach and the rate of subsequent chemical reaction. Collins and Kimball [4], and later Noyes [5], have extended the Smoluchowski theory (1917) to consider this situation (Sect. 4). In light of these quantitative theoretical models of diffusion-limited rate processes, some of the more recent and careful experiments on diffusion-controlled reactions in solution are considered briefly in Sect. 5. As the Smoluchowski theory... 

In the volume of interest are two reactants A and B in solution. B is present in considerable excess over A. The typical distance between A reactants is rAA (3/47t[A] )1/3, where [A] is the number density of A (per m3), whereas that distance between B reactants is significantly less than rAA. To an excellent approximation, the distribution of B is uniform around A. As a first guess, the density of B a large distance from A can be taken as unity and the Smoluchowski [3] or Collins and Kimball [4] analysis of the diffusion of B into A used (Chap. 2, Sects. 3 and 4). If the reactants are uncharged and the rate of reaction on encounter is large, the Smoluchowski analysis shows the density of B about A [see (eqn. (16)] to be... 

To estimate the rate constant for a reaction that is controlled strictly by the frequency of collisions of particles, we must ask how many times per second one of a number n of particles will be hit by another of the particles as a result of Brownian movement. The problem was analyzed in 1917 by Smoluchowski,30/31 who considered the rate at which a particle B diffuses toward a second particle A and disappears when the two codide. Using Fick s law of diffusion, he concluded that the number of encounters per milliliter per second was given by Eq. 9-26. 

Flocculation kinetics can be described in different ways. Here we introduce a treatment first suggested by Smoluchowski [547], and described in Ref. [538], p. 417. The formalism can also be used to treat the aggregation of sols. A prerequisite for coalescence is that droplets encounter each other and collide. Smoluchowski calculated the rate of diffusional encounters between spherical droplets of radius R. The rate of diffusion-limited encounters is SttDRc2, where c is the concentration of droplets (number of droplets per unit volume). For the diffusion coefficient D we use the Stokes-Einstein relation D = kBT/finr/R. The rate of diffusion-limited encounters is, at the same time, the upper limit for the decrease in droplet concentration. Both rates are equal when each encounter leads to coalescence. Then the rate of encounters is given by... 

The upper boundary of the reaction rate is reached when every collision between substrate and enzyme molecules leads to reaction and thus to product. In this case, the Boltzmann factor, exp(-EJRT), is equal to lin the transition-state theory equations and the reaction is diffusion-limited or diffusion-controlled (owing to the difference in mass, the reaction is controlled only by the rate of diffusion of the substrate molecule). The reaction rate under diffusion control is limited by the number of collisions, the frequency Z of which can be calculated according to the Smoluchowski equation [Smoluchowski, 1915 Eq. (2.9)]. 

Table 1. Number, weight, and z-average degrees of polymerization for the random homopolymerization of bifunctional monomer calculated using the Smoluchowski equation (Eq. 8) and expressed in terms of time (t) and conversion degree (p)...

The classical treatment of such processes derives from the consideration of the coagulation of colloids (Smoluchowski, 1917), but many accounts have been given of how the same approach can be used for diffusion-controlled reactions (Noyes, 1961 North, 1964 Moelwyn-Hughes, 1971). The starting point is the assumption of a random distribution of the two reactants (here given the symbols X and B) in the solution. Then, if B is capable of reacting on encounter with a number of molecules of X, it follows that such reactions deplete the concentration of X in the neighbourhood of B and therefore set up a... 

The rate of coagulation is considered to be dominated by a binary process involving collisions between two particles. The rate is given by bn,nj, where nl is the number of particles of z th size and b a collision parameter. For collision between i - and / -sized particles during Brownian motion, the physicist M. Smoluchowski derived the relation ... 

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