Mass diffusion with homogeneous reaction

Steady-state mass diffusion with homogeneous chemical reaction... 

In a system with homogeneous reactions (e.g. reactive absorption), mass and heat transfer is described by the following convective diffusion and convective heat conduction equations (Kenig, 2000) ... 

The mass balance with homogeneous one-dimensional diffusion and irreversible nth-order chemical reaction provides basic information for the spatial dependence of reactant molar density within a catalytic pellet. Since this problem is based on one isolated pellet, the molar density profile can be obtained for any type of chemical kinetics. Of course, analytical solutions are available only when the rate law conforms to simple zeroth- or first-order kinetics. Numerical techniques are required to solve the mass balance when the kinetics are more complex. The rationale for developing a correlation between the effectiveness factor and intrapellet Damkohler number is based on the fact that the reactor design engineer does not want to consider details of the interplay between diffusion and chemical reaction in each catalytic pellet when these pellets are packed in a large-scale reactor. The strategy is formulated as follows ... 

These intriguing situations, which are similar to the so-called "diffusion falsification" regime of fluid-porous catalytic solid systems (5), can be successfully handled by the "theory of mass transfer with chemical reaction". Indeed, they can be deployed to obtain kinetics of exceedingly fast reactions in simple apparatuses, which in the normal investigations in homogeneous systems would have required sophisticated and expensive equipment. Further, it is possible, under certain conditions, to obtain values of rate constants without knowing the solubility and diffusivity. In addition, simple experiments yield diffusivity and solubility of reactive species which would otherwise have been - indeed, if possible - extremely difficult. 

The solution procedure to this equation is the same as described for the temporal isothermal species equations described above. In addition, the associated temperature sensitivity equation can be simply obtained by taking the derivative of Eq. (2.87) with respect to each of the input parameters to the model. The governing equations for similar types of homogeneous reaction systems can be developed for constant volume systems, and stirred and plug flow reactors as described in Chapters 3 and 4 and elsewhere [31-37], The solution to homogeneous systems described by Eq. (2.81) and Eq. (2.87) are often used to study reaction mechanisms in the absence of mass diffusion. These equations (or very similar ones) can approximate the chemical kinetics in flow reactor and shock tube experiments, which are frequently used for developing hydrocarbon combustion reaction mechanisms. 

The mathematical difficulty increases from homogeneous reactions, to mass transfer, and to heterogeneous reactions. To quantify the kinetics of homogeneous reactions, ordinary differential equations must be solved. To quantify diffusion, the diffusion equation (a partial differential equation) must be solved. To quantify mass transport including both convection and diffusion, the combined equation of flow and diffusion (a more complicated partial differential equation than the simple diffusion equation) must be solved. To understand kinetics of heterogeneous reactions, the equations for mass or heat transfer must be solved under other constraints (such as interface equilibrium or reaction), often with very complicated boundary conditions because of many particles. 

Heat transfer is an extremely important factor in CVD reactor operation, particularly for LPCVD reactors. These reactors are operated in a regime in which the deposition is primarily controlled by surface reaction processes. Because of the exponential dependence of reaction rates on temperature, even a few degrees of variation in surface temperature can produce unacceptable variations in deposition rates. On the other hand, with atmospheric CVD processes, which are often limited by mass transfer, small susceptor temperature variations have little effect on the growth rate because of the slow variation of the diffusion with temperature. Heat transfer is also a factor in controlling the gas-phase temperature to avoid homogeneous nucleation through premature reactions. At the high temperatures (700-1400 K) of most... 

As is shown in Figure 2, in the two-phase model the fluid bed reactor is assumed to be divided into two phases with mass transfer across the phase boundary. The mass transfer between the two phases and the subsequent reaction in the suspension phase are described in analogy to gas/liquid reactors, i.e. as an absorption of the reactants from the bubble phase with pseudo-homogeneous reaction in the suspension phase. Mass transfer from the bubble surface into the bulk of the suspension phase is described by the film theory with 6 being the thickness of the film. D is the diffusion coefficient of the gas and a denotes the mass transfer coefficient based on unit of transfer area between the two phases. 6 is given by 6 = D/a. 

In this text, the conversion rate is used in relevant equations to avoid difficulties in applying the correct sign to the reaction rate in material balances. Note that the chemical conversion rate is not identical to the chemical reaction rate. The chemical reaction rate only reflects the chemical kinetics of the system, that is, the conversion rate measured under such conditions that it is not influenced by physical transport (diffusion and convective mass transfer) of reactants toward the reaction site or of product away from it. The reaction rate generally depends only on the composition of the reaction mixture, its temperature and pressure, and the properties of the catalyst. The conversion rate, in addition, can be influenced by the conditions of flow, mixing, and mass and heat transfer in the reaction system. For homogeneous reactions that proceed slowly with respect to potential physical transport, the conversion rate approximates the reaction rate. In contrast, for homogeneous reactions in poorly mixed fluids and for relatively rapid heterogeneous reactions, physical transport phenomena may reduce the conversion rate. In this case, the conversion rate is lower than the reaction rate. 

Many homogeneous reactions occur in the liquid phase, but consume reactants that must be supplied by mass transfer from a gas phase (or occasionally from another liquid phase). This is a typical problem of reaction engineering and is treated in some detail in most modem texts of that field [1,3,4,9,16,17]. Customarily, a power law is assumed for the rate of the chemical reaction and is then combined with a standard linear-driving force or Fickian diffusion treatment of mass transfer. A mass-transfer limitation lowers the rate, which in some extreme situations can become entirely mass transfer-controlled. Certain types of multistep reactions, however, can produce a totally different and very interesting behavior that may involve instability. 

The latter two conditions indicate that reactant concentration within the catalyst vanishes at the critical spatial coordinate when 0 < criticai < H and it does so with a zero slope. Conditions 2a and 3 are reasonable because reactant A will not diffuse further into the catalyst, to smaller values of r), if it exhibits zero flux at ]criticai. When / critical < 0, couditiou 2b must be employed, which is consistent with the well-known symmetry condition at the center of the catalyst for kinetic rate laws where lEl constant. Zeroth-order reactions are unique because they require one to implement a method of turning ofF the rate of reaction when no reactants are present. Obviously, a zeroth-order rate law always produces the same rate of reaction because reactant molar densities do not appear explicitly in the chemical reaction term. Hence, the mass balance for homogeneous onedimensional diffusion and zeroth-order chemical reaction is solved only over the following range of the independent variable criticai < < 1. when Jiciiacai is... 

The homogeneous diffusion model is slightly more complex in cyUndrical coordinates relative to the model described above in rectangular coordinates. Additional complexity arises because the radial term of the Laplacian operator (V V = V ) accounts for the fact that the surface area across which radial diffusion occurs increases linearly with dimensionless coordinate r/ as one moves radially outward. Basic information for = f(t]) is obtained by integrating the dimensionless mass balance with radial diffusion and chemical reaction ... 

Solve the dimensionless mass transfer equation (i.e., the mass balance for reactant A) with homogeneous one-dimensional diffusion and zeroth-order irreversible chemical reaction to obtain an expression for 4molar density of reactant A. 

Heterogeneous electrode reactions can be compared with homogeneous kinetics in solution, with regard to mass transport. The second-order rate coefficient for a fast homogeneous reactions in solution, k(hom), which would be observed if diffusion were infinitely fast, can be related to the measured rate coefficient, kob3(hom) by application of Eick s first law in a spherical continuum diffusion field around the reacting molecule. At a collision distance Tab. this corresponds to the average... 

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