Kinetic Models and Single-Component Problems

1 Solution of the Breakthrough Curve under Constant Pattern Condition. . 653 

6 Properties of the Shock Layer Thickness in Frontal Analysis.662 

1 Solution of the Reaction-Kinetic Model in the Case of a Step Injection.670 

2 Numerical Solutions of the Kinetic Model for a Breakthrough Curve.671 

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In linear chromatography, these last two linear kinetic models are particular cases of the model used by Lapidus and Amundson [85] (Eq. 2.22). By contrast, the different lumped kinetic models give different solutions in nonlinear chromatography. Investigations of the properties of these models and especially of the relationship between the band profiles and the value of the kinetic constant have been carried out for many single-component problems. Numerous studies of the influence of the mass transfer kinetics on the separation of binary mixture have been published in the last ten years. These results are discussed in Chapters 14 and 16, respectively. 

Furthermore, the theoretical analysis of the single-component problem in the ideal model provides some of the fimdamental concepts in nonlinear chromatography, such as the notions of the velocity associated with a concentration, of concentration shocks, and of diffuse bormdaries [1,2]. It also provides an understanding of the relationship between the thermod5mamics of phase equilibria, the shape of the isotherm (i.e., convex upward, linear, convex downward, or S-shaped) and the band profiles. Finally, it provides an explanation of the relative importance of the influences of the thermodynamics and the kinetics on the band profile. These concepts will provide a most useful framework for imderstanding the phenomena that occur in preparative chromatography. 

All cases of practical importance in liquid chromatography deal with the separation of multicomponent feed mixtures. As shown in Chapter 2, the combination of the mass balance equations for the components of the feed, their isotherm equations, and a chromatography model that accounts for the kinetics of mass transfer between the two phases of the system permits the calculation of the individual band profiles of these compounds. To address this problem, we need first to understand, measure, and model the equilibrium isotherms of multicomponent mixtures. These equilibria are more complex than single-component ones, due to the competition between the different components for interaction with the stationary phase, a phenomenon that is imderstood but not yet predictable. We observe that the adsorption isotherms of the different compounds that are simultaneously present in a solution are almost always neither linear nor independent. In a finite-concentration solution, the amount of a component adsorbed at equilib-... 

In Chapter 14, we discussed the case of a single-component band. In practice, there are almost always several components present simultaneously, and they have different mass transfer properties. As seen in Chapter 4, the equilibrium isotherms of the different components of a mixture depend on the concentrations of all the components. Thus, as seen in Chapters 11 to 13, the mass balances of the different components are coupled, which makes more complex the solution of the multicomponent kinetic models. Because of the complexity of these models, approximate analytical solutions can be obtained only under the assumption of constant pattern conditions. In all other cases, only numerical solutions are possible. The problem is further complicated because the diffusion coefficients and the rate constants depend on the concentrations of the corresponding components and of all the other feed components. However, there are still relatively few papers that discuss this second form of coupling between component band profiles in great detail. In most cases, the investigations of mass transfer kinetics and the use of the kinetic models of chromatography in the literature assume that the rate constants and the diffusion coefficients are concentration independent. This seems to be an acceptable first-order approximation in many cases, albeit separation problems in which more sophisticated theoretical approaches are needed begin to appear as the accuracy of measru ments improve and more interest is paid to complex... 

Inadequate stoichiometry and poor calibration of the analytical device are interconnected problems. The kinetic model itself follows the stoichiometric rules, but an inadequate calibration of the analytical instrument causes systematic deviations. This can be illustrated with a simple example. Assume diat a bimolecular reaction, A + B P, is carried out in a liquid-phase batch reactor. The density of the reaction mixture is assumed to be constant. The reaction is started with A and B, and no P is present in the initial mixture. The concentrations are related by cp=CoA-Cj=Cob -Cb, i e. produced product, P, equals with consumed reactant. If the concentration of the component B has a calibration error, we get instead of the correct concentration cb an erroneous one, c n ncs, which does not fulfil the stoichiometric relation. If the error is large for a single component, it is easy to recognize, but the situation can be much worse calibration errors are present in several components and all of their effects are spread during nonlinear regression, in the estimation of the model parameters. This is reflected by the fact that the total mass balance is not fulfilled by the experimental data. A way to check the analytical data is to use some fonns of total balances, e.g. atom balances or total molar amounts or concentrations. For example, for the model reaction, A + B P, we have the relation ca+cb+cp -c()a+c0 -constant (again c0p=0). 

Adsorption kinetics of a single particle (activated carbon type) is dealt with in Chapter 9, where we show a number of adsorption / desorption problems for a single particle. Mathematical models are presented, and their parameters are carefully identified and explained. We first start with simple examples such as adsorption of one component in a single particle under isothermal conditions. This simple example will bring out many important features that an adsorption engineer will need to know, such as the dependence of adsorption kinetics behaviour on many important parameters such as particle size, bulk concentration, temperature, pressure, pore size and adsorption affinity. We then discuss the complexity in the dealing with multicomponent systems whereby governing equations are usually coupled nonlinear differential equations. The only tool to solve these equations is... 

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