Smoluchowski equations

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)]. 

Equation (B.IO) is termed the Chapman-Kolmogorov equation and Eq. (B.ll) the Smoluchowski equation (Smoluchowski s integral equation). 

Henry Equation A relation expressing the proportionality between electrophoretic mobility and zeta potential for different values of the Debye length and size of the species. See also Electrophoresis, Hiickel Equation, Smoluchowski Equation. 

The theoretical treatment of the dynamics of a polymer chain in solution usually starts by writing down Kirkwood s diffusion equation (Smoluchowski equation) ... 

Using W2 = 17jP2, (A3.2.81 and (A3.2.9) may be used to satisfy the Smoluchowski equation, (A3.2.2). another necessary property for a stationary process. Thus u(t) is an example of a stationary Gaussian-Markov... 

Smoluchowski theory [29, 30] and its modifications fonu the basis of most approaches used to interpret bimolecular rate constants obtained from chemical kinetics experiments in tenus of difhision effects [31]. The Smoluchowski model is based on Brownian motion theory underlying the phenomenological difhision equation in the absence of external forces. In the standard picture, one considers a dilute fluid solution of reactants A and B with [A] [B] and asks for the time evolution of [B] in the vicinity of A, i.e. of the density distribution p(r,t) = [B](rl)/[B] 2i ] r(t))l ] Q ([B] is assumed not to change appreciably during the reaction). The initial distribution and the outer and inner boundary conditions are chosen, respectively, as... 

Diflfiision-controlled reactions between ions in solution are strongly influenced by the Coulomb interaction accelerating or retarding ion diffiision. In this case, die dififiision equation for p concerning motion of one reactant about the other stationary reactant, the Debye-Smoluchowski equation. 

This ensures the correct connection between the one-dimensional Kramers model in the regime of large friction and multidimensional imimolecular rate theory in that of low friction, where Kramers model is known to be incorrect as it is restricted to the energy diflfiision limit. For low damping, equation (A3.6.29) reduces to the Lindemann-Flinshelwood expression, while in the case of very large damping, it attains the Smoluchowski limit... 

In a homogeneous system, tire rate of mixing is governed by Smoluchowski s equations [77], according to which tire diffusion-limited association rate of S and L (equation (C2.14.13)), supposed uncharged, equals tliat of tire flux and is... 

According to Smoluchowski s theory (equation 6.53), the agglomeration rate increases proportional with the fluid shear rate 7... 

Using a Smoluchowski rate-equation approach [71], we can write a system of nonlinear differential equations... 

The temperature dependence of a diffusion-controlled rate constant is very small. Actually, it is just the temperature coefficient of the diffusion coefficient, as we see from the von Smoluchowski equation. Typically, Ea for diffusion is about 8-14 kJ mol"1 (2-4 kcal mol-1) in solvents of ordinary viscosity. 

The von Smoluchowski equation must be corrected when the partners are ions to account for attractive or repulsive forces. They can be approximated by an electrostatic model. The quantity by which Eq. (9-10) or (9-13) is to be multiplied is... 

Perrin model and the Johansson and Elvingston model fall above the experimental data. Also shown in this figure is the prediction from the Stokes-Einstein-Smoluchowski expression, whereby the Stokes-Einstein expression is modified with the inclusion of the Ein-stein-Smoluchowski expression for the effect of solute on viscosity. Penke et al. [290] found that the Mackie-Meares equation fit the water diffusion data however, upon consideration of water interactions with the polymer gel, through measurements of longitudinal relaxation, adsorption interactions incorporated within the volume averaging theory also well described the experimental results. The volume averaging theory had the advantage that it could describe the effect of Bis on the relaxation within the same framework as the description of the diffusion coefficient. 

In order to describe the effects of the double layer on the particle motion, the Poisson equation is used. The Poisson equation relates the electrostatic potential field to the charge density in the double layer, and this gives rise to the concepts of zeta-potential and surface of shear. Using extensions of the double-layer theory, Debye and Huckel, Smoluchowski,... 

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 ... 

Qian and Bau [144] have analyzed such electroosmotic flow cells with embedded electrodes on the basis of the Stokes equation with Helmholtz-Smoluchowski boimdary conditions on the channel walls. They considered electrode arrays with a certain periodicity, i.e. after k electrodes the imposed pattern of electric potentials repeats itself An analytic solution of the Stokes equation was obtained in the form of a Eourier series. Specifically, they analyzed the electroosmotic flow patterns with regard to mixing applications. A simple recirculating flow pattern such as the one... 

The equations of the electrokinetic processes were derived in 1903 by the Polish physicist Maryan Ritter von Smoluchowski on the basis of ideas concerning the function of EDL in these processes that had been developed by H. Helmholtz in 1879. These equations are often called the Helmholtz-Smoluchowski equations. 

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. 

Analytical approaches to obtain the agglomerate size distribution are possible for well-mixed systems and when the rate of aggregation of clusters is defined by simple functions. In general, irreversible aggregation in well-mixed systems is described by Smoluchowski s coagulation equation, which... 

Smoluchowski s equation, like the fragmentation equation, can be written in terms of the scaling distribution. Furthermore, general forms may be determined for the tails of the scaling distribution—limits of small mass, xls(t) < 1, and large mass, x/s(t) > 1. The details can be found in van Dongen and Ernst (1988). 

This can be done by developing equations for the moments—for example, multiplying Smoluchowski s equation by xfdx, integrating from 0 to infinity, and manipulating the limits of integration yields (Hansen and Ottino, 1996b) ... 

We first consider the stmcture of the rate constant for low catalyst densities and, for simplicity, suppose the A particles are converted irreversibly to B upon collision with C (see Fig. 18a). The catalytic particles are assumed to be spherical with radius a. The chemical rate law takes the form dnA(t)/dt = —kf(t)ncnA(t), where kf(t) is the time-dependent rate coefficient. For long times, kf(t) reduces to the phenomenological forward rate constant, kf. If the dynamics of the A density field may be described by a diffusion equation, we have the well known partially absorbing sink problem considered by Smoluchowski [32]. To determine the rate constant we must solve the diffusion equation... 

The transport of dissolved species in a solvent occurs randomly through movement of the Brownian type. The particles of the dissolved substance and of the solvent continuously collide and thus move stochastically with various velocities in various directions. The relationship between the mobility of a particle, the observation time r and the mean shift (jc2) is given by the Einstein-Smoluchowski equation (in three-dimensional case)... 

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