Laws time-dependent diffusion equation

This partial differential equation is known as Pick s second law. It is the basis for the treatment of most time-dependent diffusion problems in electrochemistry. 

Most time-dependent diffusion problems in electrochemistry are governed by Fick s Second Law of diffusion. Pick s law is in the form of a differential equation, which implies that it describes what is common to aU diffusion problems and not just the characteristics of a particular diffusion problem. Fundamentally, the concentration of a species (in this case, ions in solution and near the boundary layer) is a function of position and time... 

Hence, the current (at any time) is proportional to the concentration gradient of the electroactive species. As indicated by the above equations, the dififusional flux is time dependent. Such dependence is described by Fick s second law (for linear diffusion) ... 

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... 

In the literature there are several, mostly just slightly different, equations that describe the rate coefficient of the diffusion controlled reactions these equations are usually based on the solutions of Pick II diffusion law assuming that the reaction probability at contact distance is 1. Andre et al. [131] used the following equation to describe the time dependence of excited molecule concentration [RH ] produced by an infinite excitation pulse ... 

Fick s second law (Eq. 18-14) is a second-order linear partial differential equation. Generally, its solutions are exponential functions or integrals of exponential functions such as the error function. They depend on the boundary conditions and on the initial conditions, that is, the concentration at a given time which is conveniently chosen as t = 0. The boundary conditions come in different forms. For instance, the concentration may be kept fixed at a wall located atx0. Alternatively, the wall may be impermeable for the substance, thus the flux at x0 is zero. According to Eq. 18-6, this is equivalent to keeping dC/dx = 0 at x0. Often it is assumed that the system is unbounded (i.e., that it extends from x = - °o to + °°). For this case we have to make sure that the solution C(x,t) remains finite when x -a °°. In many cases, solutions are found only by numerical approximations. For simple boundary conditions, the mathematical techniques for the solution of the diffusion equation (such as the Laplace transformation) are extensively discussed in Crank (1975) and Carslaw and Jaeger (1959). 

The diffusion equation is the partial-differential equation that governs the evolution of the concentration field produced by a given flux. With appropriate boundary and initial conditions, the solution to this equation gives the time- and spatial-dependence of the concentration. In this chapter we examine various forms assumed by the diffusion equation when Fick s law is obeyed for the flux. Cases where the diffusivity is constant, a function of concentration, a function of time, or a function of direction are included. In Chapter 5 we discuss mathematical methods of obtaining solutions to the diffusion equation for various boundary-value problems. 

Therefore, any result that follows from considerations of the form of Fick s second law applies to evolution of heat as well as concentration. However, the thermal and mass diffusion equations differ physically. The mass diffusion equation, dc/dt = V DVc, is a partial-differential equation for the density of an extensive quantity, and in the thermal case, dT/dt = V kVT is a partial-differential equation for an intensive quantity. The difference arises because for mass diffusion, the driving force is converted from a gradient in a potential V/u to a gradient in concentration Vc, which is easier to measure. For thermal diffusion, the time-dependent temperature arises because the enthalpy density is inferred from a temperature measurement. 

The equation for the time development of macroscopic concentrations formally coincides with the law of mass action but with dimensionless reaction rate K(t) = K(t)/ AnDr ) which is, generally speaking, time-dependent and defined by the flux of the dissimilar particles via the recombination sphere of the radius tq, equation (5.1.51). Using dimensionless units n(t) = 4nrln(t), r = t/tq, t = Dt/r, and the condition of the reflection of similar particles upon collisions, equation (5.1.40) (zero flux through origin), we obtain for the joint correlation functions the equations (6.3.2), (6.3.3). Note that we use the dimensionless diffusion coefficients, a = 2k, IDb = 2(1 — k), k = Da/ Da + Dq) entering equation (6.3.2). 

Sufficient DO data were not obtained from basalt-synthetic Grande Ronde groundwater experiments to allow determination of a definitive rate law. A first order kinetic model with respect to DO concentration was assumed. Rate control by diffusion kinetics and by surface-reaction mechanisms result in solution composition cnanges with different surface area and time dependencies (32,39). Therefore, by varying reactant surface area, determination of the proper functional form of the integrated rate equation for basalt-water redox reactions is possible. 

Derive the Cottrell equation by combining Fick s first law of diffusion with the time-dependent change of the concentration gradient during a potential step experiment. 

In Example 10.1 the case where the aerosol concentration does not change with time was considered. In many practical situations, however, the aerosol concentration does change with time, possibly as a result of diffusion and subsequent loss of particles to a wall or other surface. In this event, Fick s second law, Eq. 9.2, must be used. Solution of this equation is possible in many cases, depending on the initial and boundary conditions chosen, although the solutions generally take on very complex forms and the actual mechanics involved to find these solutions can be quite tedious. Fortunately, there are several excellent books available which contain large numbers of solutions to the transient diffusion equation (Barrer, 1941 Jost, 1952). Thus, in most cases it is possible to fit initial and boundary conditions of an aerosol problem to one of the published solutions. Several commonly occurring examples follow. 

The experimental technique controls how the mass transport and rate law are combined (and filtered, e.g. by removing convective transport terms in a diffusion-only CV experiment) to form the overall material balance equation. Migration effects may be eliminated by addition of supporting electrolyte steady-state measurements eliminate the need to solve the equation in a time-dependent manner excess substrate can reduce the kinetics from second to pseudo-first order in a mechanism such as EC. The material balance equations (one for each species), with a given set of boundary conditions and parameters (electrode/cell dimensions, flow rate, rate constants, etc.), define an I-E-t surface, which is traversed by the voltammetric technique. 

Concentration is variable with time, Pick s second law Most interactions involving mass transfer between the packaging and food behave under non-steady state conditions and are referred to as migration. A number of solutions exist by integration of the diffusion equation 8.7 that are dependent on the so-called initial and boundary conditions of special applications. Many solutions are taken from analogous solutions of the heat conductance equation that has been known for many years ... 

Next, Fig. 5 shows a typical center of mass trajectory for the case of a full chaotic internal phase space. The eyecatching new feature is that the motion is no more restricted to some bounded volume of phase space. The trajectory of the CM motion of the hydrogen atom in the plane perpendicular to the magnetic field now closely resembles the random motion of a Brownian particle. In fact, the underlying equation of motion at Eq. (35) for the CM motion is a Langevin-type equation without friction. The corresponding stochastic Lan-gevin force is replaced by our intrinsic chaotic force — e B x r). A main characteristic of random Brownian motion is the diffusion law, i.e. the linear dependence of the travelled mean-square distance on time. We have plotted in Fig. 6 for our case of a chaotic force for 500 CM trajectories the mean-square distance as a function of time. Within statistical accuracy the plot shows a linear dependence. The mean square distance

of the CM after time t, therefore, obeys the diffusion equation... 

The coupling of the flux and the time dependence of the counter-ion concentration is achieved through the material balance condition and Pick s Second Law (often termed the condition of continuity). For spherical particles and a constant interdifjusion coefficient, D, the foregoing considerations give the following partial differential equation for particle diffusion kinetics ... 

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