Liquid-solid kinetic processes

The first half of this textbook introduced the basic tools needed to understand most kinetic processes. Specifically, we learned how to calculate the main thermodynamic driving forces behind kinetic transformations (Chapter 2), we learned how to calculate the rates of reaction processes (Chapter 3), and we learned how to calculate the rates of transport processes (Chapter 4). In the second half of this textbook, we will use these tools to model and understand a number of real-world kinetic processes involving gas-solid, solid-liquid, and solid-solid transformations. In this chapter, we begin with gas-solid kinetic processes. 

Chemical reactions obey the rules of chemical kinetics (see Chapter 2) and chemical thermodynamics, if they occur slowly and do not exhibit a significant heat of reaction in the homogeneous system (microkinetics). Thermodynamics, as reviewed in Chapter 3, has an essential role in the scale-up of reactors. It shows the form that rate equations must take in the limiting case where a reaction has attained equilibrium. Consistency is required thermodynamically before a rate equation achieves success over tlie entire range of conversion. Generally, chemical reactions do not depend on the theory of similarity rules. However, most industrial reactions occur under heterogeneous systems (e.g., liquid/solid, gas/solid, liquid/gas, and liquid/liquid), thereby generating enormous heat of reaction. Therefore, mass and heat transfer processes (macrokinetics) that are scale-dependent often accompany the chemical reaction. The path of such chemical reactions will be... 

Section 8 deals with reactions which occur at gas—solid and solid—solid interfaces, other than the degradation of solid polymers which has already been reviewed in Volume 14A. Reaction at the liquid—solid interface (and corrosion), involving electrochemical processes outside the coverage of this series, are not considered. With respect to chemical processes at gas-solid interfaces, it has been necessary to discuss surface structure and adsorption as a lead-in to the consideration of the kinetics and mechanism of catalytic reactions. 

Semibatch reactors are often used to mn highly exothermic reactions isothermally, to run gas-liquid(-solid) processes isobarically, and to prevent dangerous accumulation of some reactants in the reaction mixture. Contrary to batch of)eration, temperature and pressure in semibatch reactors can be varied independently. The liquid reaction mixture can be considered as ideally mixed, while it is assumed that the introduced gas flows up like a piston (certainly this is not entirely true). Kinetic modelling of semibatch experiments is as difficult as that of batch, non-isotherma experiments. 

Laboratory reactors for studying gas-liquid processes can be classified as (1) reactors for which the hydrodynamics is well known or can easily be determined, i.e. reactors for which the interfacial area, a, and mass-transfer coefficients, ki and kc, are known (e.g. the laminar jet reactor, wetted wall-column, and rotating drum, see Fig. 5.4-21), and (2) those with a well-defined interfacial area and ill-determined hydrodynamics (e.g. the stirred-cell reactor, see Fig. 5.4-22). Reactors of these two types can be successfully used for studying intrinsic kinetics of gas-liquid processes. They can also be used for studying liquid-liquid and liquid-solid processes. 

The equipment required to develop this type of sensor is very simple and resembles closely that used to implement ordinary liquid-solid separations in FI manifolds. The only difference lies in the replacement of the packed reactor located in the transport-reaction zone with a packed (usually photometric or fluorimetric) flow-cell accommodated in the detector. Whether the packing material is inert or active, it should meet the following requirements (a) its particle diameter should be large enough (< 80-100 fim) to avoid overpressure (b) it should be made of a material compatible with the nature of the integrated detection system e.g. almost transparent for absorbance measurements) and, (c) the retention/elution process should be fast enough to avoid kinetic problems. 

Due to the fact that industrial composites are made up of combinations of metals, polymers, and ceramics, the kinetic processes involved in the formation, transformation, and degradation of composites are often the same as those of the individual components. Most of the processes we have described to this point have involved condensed phases—liquids or solids—but there are two gas-phase processes, widely utilized for composite formation, that require some individualized attention. Chemical vapor deposition (CVD) and chemical vapor infiltration (CVI) involve the reaction of gas phase species with a solid substrate to form a heterogeneous, solid-phase composite. Because this discussion must necessarily involve some of the concepts of transport phenomena, namely diffusion, you may wish to refresh your memory from your transport course, or refer to the specific topics in Chapter 4 as they come up in the course of this description. 

A vast number of engineering materials are used in solid form, but during processing may be found in vapor or liquid phases. The vapor— solid (condensation) and liquid—>solid (solidification) transformations take place at a distinct interface whose motion determines the rate of formation of the solid. In this chapter we consider some of the factors that influence the kinetics of vapor/solid and liquid/solid interface motion. Because vapor and liquid phases lack long-range structural order, the primary structural features that may influence the motion of these interfaces are those at the solid surface. 

The defects generated in ion—solid interactions influence the kinetic processes that occur both inside and outside the cascade volume. At times long after the cascade lifetime (t > 10-11 s), the remaining vacancy—interstitial pairs can contribute to atomic diffusion processes. This process, commonly called radiation enhanced diffusion (RED), can be described by rate equations and an analytical approach (27). Within the cascade itself, under conditions of high defect densities, local energy depositions exceed 1 eV/atom and local kinetic processes can be described on the basis of a liquid-like diffusion formalism (28,29). 

By the use of various transient methods, electrochemistry has found extensive new applications for the study of chemical reactions and adsorption phenomena. Thus a combination of thermodynamic and kinetic measurements can be utilized to characterize the chemistry of heterogeneous electron-transfer reactions. Furthermore, heterogeneous adsorption processes (liquid-solid) have been the subject of intense investigations. The mechanisms of metal ion com-plexation reactions also have been ascertained through the use of various electrochemical impulse techniques. 

Another classification of chemical reactors is according to the phases being present, either single phase or multiphase reactors. Examples of multiphase reactors are gas liquid, liquid-liquid, gas solid or liquid solid catalytic reactors. In the last category, all reactants and products are in the same phase, but the reaction is catalysed by a solid catalyst. Another group is gas liquid solid reactors, where one reactant is in the gas phase, another in the liquid phase and the reaction is catalysed by a solid catalyst. In multiphase reactors, in order for the reaction to occur, components have to diffuse from one phase to another. These mass transfer processes influence and determine, in combination with the chemical kinetics, the overall reaction rate, i.e. how fast the chemical reaction takes place. This interaction between mass transfer and chemical kinetics is very important in chemical reaction engineering. Since chemical reactions either produce or consume heat, heat removal is also very important. Heat transfer processes determine the reaction temperature and, hence, influence the reaction rate. 

For example, when we consider the design of specialty chemical, polymer, biological, electronic materials, etc. processes, the separation units are usually described by transport-limited models, rather than the thermodynamically limited models encountered in petrochemical processes (flash drums, plate distillations, plate absorbers, extractions, etc.). Thus, from a design perspective, we need to estimate vapor-liquid-solid equilibria, as well as transport coefficients. Similarly, we need to estimate reaction kinetic models for all kinds of reactors, for example, chemical, polymer, biological, and electronic materials reactors, as well as crystallization kinetics, based on the molecular structures of the components present. Furthermore, it will be necessary to estimate constitutive equations for the complex materials we will encounter in new processes. 

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