Rate coefficient diffusive

The dialytic regime is characterized by high surface reaction rate coefficients and by rate-limiting diffusion. The Sherwood number (Sh) characterizes the regimes. Sh is defined as the ratio of the driving force for diffusion in the boundary layer to the driving force for surface reaction alternatively, it is the ratio of the resistivity for diffusion to the resistivity for chemical reaction (reciprocal reaction rate coefficient). Diffusion limitation is the regime at Sh 1 and reaction limitation means Sh 1. The Sherwood number is closely related to the Biot, Nusselt, and Damkohler II numbers and the Thiele modulus. Some call it the CVD number. In the boundary-layer model it is a simple function of the thickness of the boundary layer, the diffusion coefficient, and the reaction rate coefficient. For simplicity a first-order reaction will be considered in the derivation below. 

The rate of dissolving of a solid is determined by the rate of diffusion through a boundary layer of solution. Derive the equation for the net rate of dissolving. Take Co to be the saturation concentration and rf to be the effective thickness of the diffusion layer denote diffusion coefficient by . 

The main conclusion to be drawn from these studies is that for most practical purposes the linear rate model provides an adequate approximation and the use of the more cumbersome and computationally time consuming diffusing models is generally not necessary. The Glueckauf approximation provides the required estimate of the effective mass transfer coefficient for a diffusion controlled system. More detailed analysis shows that when more than one mass transfer resistance is significant the overall rate coefficient may be estimated simply from the sum of the resistances (7) ... 

As a reactant molecule from the fluid phase surrounding the particle enters the pore stmcture, it can either react on the surface or continue diffusing toward the center of the particle. A quantitative model of the process is developed by writing a differential equation for the conservation of mass of the reactant diffusing into the particle. At steady state, the rate of diffusion of the reactant into a shell of infinitesimal thickness minus the rate of diffusion out of the shell is equal to the rate of consumption of the reactant in the shell by chemical reaction. Solving the equation leads to a result that shows how the rate of the catalytic reaction is influenced by the interplay of the transport, which is characterized by the effective diffusion coefficient of the reactant in the pores, and the reaction, which is characterized by the first-order reaction rate constant. 

The gas-phase rate coefficient fcc is not affecded by the fact that a chemic reaction is taking place in the liquid phase. If the liquid-phase chemical reaction is extremely fast and irreversible, the rate of absorption may be governed completely by the resistance to diffusion in the gas phase. In this case the absorption rate may be estimated by knowing only the gas-phase rate coefficient fcc of else the height of one gas-phase transfer unit Hq =... 

Principles of Rigorous Absorber Design Danckwerts and Alper [Trans. Tn.st. Chem. Eng., 53, 34 (1975)] have shown that when adequate data are available for the Idnetic-reaciion-rate coefficients, the mass-transfer coefficients fcc and /c , the effective interfacial area per unit volume a, the physical solubility or Henry s-law constants, and the effective diffusivities of the various reactants, then the design of a packed tower can be calculated from first principles with considerable precision. 

Example 8 Estimation of Rate Coejficient Estimate the rate coefficient for flow of a 0.01-M water solution of NaCl through a bed of cation exchange particles in hydrogen form with e = 0.4. The superficial velocity is 0.2 cm/s and the temperature is 25 C. The particles are 600 im in diameter, and the diffusion coefficient of sodium ion is 1.2 X 10 cmVs in solution and 9.4 X 10 cmVs inside the particles (of. Table 16-8). The bulk density is 0.7 g dry resin/cnd of bed, and the capacity of the resin is 4.9 mequiv/g dry resin. The mass action eqiiihbrium constant is 1.5. 

At high temperatures there is experimental evidence tlrat the Anhenius plot for some metals is curved, indicating an increased rate of diffusion over tlrat obtained by linear exU apolation of tire lower temperature data. This effect is interpreted to indicate enhanced diffusion via divacancies, rather tlrair single vacaircy-atom exchange. The diffusion coefficient must now be represented by an Anheirius equation in the form... 

Inert gas pressure does not have any effect on the surface catalysis controlling the rate. If diffusion is slowing down the rate, high inert gas pressure will cut the diffusion coefficient and the rate will be less than at low Pi. If both this and a low energy of activation is are observed, a difflisional effect is very likely. 

Center of mass or translational diffusion is believed to be the rate-determining step for small radicals33 and may also be important for larger species. However, other diffusion mechanisms are operative and are required to bring ihe chain ends together and these will often be the major term in the termination rate coefficient for the case of macromolecular species. These include ... 

In dealing with radical-radical termination in bulk, polymerization it is common practice to divide the polymerization timeline into three or more conversion regimes.2 "0 The reason for this is evident from Figure 5.3. Within each regime, expressions for the termination rate coefficient are defined according to the dominant mechanism for chain end diffusion. The usual division is as follows ... 

Most in depth studies of termination deal only with the low conversion regime. Logic dictates that simple center of mass diffusion and overall chain movement by reptation or many other mechanisms will be chain length dependent. At any instant, the overall rate coefficient for termination can be expressed as a weighted average of individual chain length dependent rate coefficients (eq. 20) 39... 

This deceleratory reaction obeyed the parabolic law [eqn. (10)] attributed to diffusion control in one dimension, normal to the main crystal face. E and A values (92—145 kJ mole-1 and 109—10,s s-1, respectively) for reaction at 490—520 K varied significantly with prevailing water vapour pressure and a plot of rate coefficient against PH2o (most unusually) showed a double minimum. These workers [1269] also studied the decomposition of Pb2Cl2C03 at 565—615 K, which also obeyed the parabolic law at 565 K in nitrogen but at higher temperatures obeyed the Jander equation [eqn. (14)]. Values of E and A systematically increased... 

The retarding influence of the product barrier in many solid—solid interactions is a rate-controlling factor that is not usually apparent in the decompositions of single solids. However, even where diffusion control operates, this is often in addition to, and in conjunction with, geometric factors (i.e. changes in reaction interfacial area with a) and kinetic equations based on contributions from both sources are discussed in Chap. 3, Sect. 3.3. As in the decompositions of single solids, reaction rate coefficients (and the shapes of a—time curves) for solid + solid reactions are sensitive to sizes, shapes and, here, also on the relative dispositions of the components of the reactant mixture. Inevitably as the number of different crystalline components present initially is increased, the number of variables requiring specification to define the reactant completely rises the parameters concerned are mentioned in Table 17. 

One facet of kinetic studies which must be considered is the fact that the observed reaction rate coefficients in first- and higher-order reactions are assumed to be related to the electronic structure of the molecule. However, recent work has shown that this assumption can be highly misleading if, in fact, the observed reaction rate is close to the encounter rate, i.e. reaction occurs at almost every collision and is limited only by the speed with which the reacting entities can diffuse through the medium the reaction is then said to be subject to diffusion control (see Volume 2, Chapter 4). It is apparent that substituent effects derived from reaction rates measured under these conditions may or will be meaningless since the rate of substitution is already at or near the maximum possible. 

Low energy ion-molecule reactions have been studied in flames at temperatures between 1000° and 4000 °K. and pressures of 1 to 760 torr. Reactions of ions derived from hydrocarbons have been most widely investigated, and mechanisms developed account for most of the ions observed mass spectrometrically. Rate constants of many of the reactions can be determined. Emphasis is on the use of flames as media in which reaction rate coefficients can be measured. Flames provide environments in which reactions of such species as metallic and halide additive ions may also be studied many interpretations of these studies, however, are at present speculative. Brief indications of the production, recombination, and diffusion of ions in flames are also provided. 

Obviously, construction of a mathematical model of this process, with our present limited knowledge about some of the critical details of the process, requires good insight and many qualitative judgments to pose a solvable mathematical problem with some claim to realism. For example what dictates the point of phase separation does equilibrium or rate of diffusion govern the monomer partitioning between phase if it is the former what are the partition coefficients for each monomer which polymeric species go to each phase and so on. 

Diffusion of the fluid into the bulk. Rates of diffusion are governed by Pick s laws, which involve concentration gradient and are quantified by the diffusion coefficient D these are differential equations that can be integrated to meet many kinds of boundary conditions applying to different diffusive processes. ... 

Rate of Formation of Primary Precursors. A steady state radical balance was used to calculate the concentration of the copolymer oligomer radicals in the aqueous phase. This balance equated the radical generation rate with the sum of the rates of radical termination and of radical entry into the particles and precursors. The calculation of the entry rate coefficients was based on the hypothesis that radical entry is governed by mass transfer through a surface film in parallel with bulk diffusion/electrostatic attraction/repulsion of an oligomer with a latex particle but in series with a limiting rate determining step (Richards, J. R. et al. J. AppI. Polv. Sci.. in press). Initiator efficiency was... 

The disadvantage of the fluid model is that no kinetic information is obtained. Also, transport (diffusion, mobility) and rate coefficients (ionization, attachment) are needed, which can only be obtained from experiments or from kinetic calculations in simpler settings (e.g. Townsend discharges). Experimental data on... 

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