Heterogeneous catalysis first-order chemical reaction

In some cases, adsorption of analyte can be followed by a chemical reaction. The Langmuir-Hinshelwood (LH) and power-law models have been used successfully in describing the kinetics of a broad range of gas-solid reaction systems [105,106]. The LH model, developed to describe interactions between dissimilar adsorbates in the context of heterogeneous catalysis [107], assumes that gas adsorption follows a Langmuir isotherm and that the adsorbates are sufficiently mobile so that they equilibrate with one another on the surface on a time scale that is rapid compared to desorpticm. The power-law model assumes a Fre-undlich adsorption isotherm. Bodi models assume that the surface reaction is first-order with respect to the reactant gas, and that surface coverage asymptotically approaches a mmiolayer widi increasing gas concentration. 

Figure 12-5 (a) Effectiveness factor plot for nth-order kinetics spherical catalyst particles (from Mass Transfer in Heterogeneous Catalysis, hy C. N. Satterfield, 1970 reprint edition Robert E. Krieger Publishing Co., 1981 reprinted by permission of the author), (b) First-order reaction in different pellet geometries (from R. Aris, Introduction to the Analysis of Chemical Reactors, 1965, p. 131 reprinted by permission of Prentice-Hall, Englewood Cliffs, NJ)... 

When a chemical intermediate step in an overall electrochemical reaction sequence is rate determining, for example, an adsorbed radical recombination step or a first-order dissociation step involving an adsorbed intermediate [e.g., of RCOO in the Kolbe reaction (75)], then the general principles of heterogeneous catalysis do apply more or less in the usual way. However, even then, at an electrode, it must be noted that its surface is populated also and ubiquitously by oriented adsorbed solvent molecules (2, i) and by anions or cations of the electrolyte (7). The concentrations and orientational states of these species are normally dependent on electrode potential or interfacial field (7-i). 

The present paper (just as previous ones, references 2-6) considers the thermal mechanism as being responsible for the formation of DSs. In other words, the factor of nonlinearity is here the exponential dependence of the reaction heat generation intensity on temperature, which is the commonest in chemistry, and the concentration-velocity relation corresponds to the linear case of a first-order reaction. Consideration of the chemically simplest case aims at forming a basis of the theory of DS in heterogeneous catalysis and its further development by consistently complicating the kinetic law of a reaction and introducing into the model nonlinearities (feedbacks) of both... 

The adsorption/desorption equilibrium constant for each component is Kf = 0.25 atm and forward is the kinetic rate constant for the forward chemical reaction on the catalytic surface with units of moles per area per time. The reason that forward has the same units as Ehw is because rate laws for heterogeneous catalysis are written in terms of fractional surface coverage by the adsorbed species that participate in the reaction. Langmuir isotherms are subsequently used to express fractional surface coverage of the reacting species in terms of their partial pressures. The best value for the pseudo-first-order kinetic rate constant is calculated from... 

Until now, we have only considered chemical reactions in homogeneous systems. However, the study of heterogeneous systems, in which more than one phase is present, are equally important, particularly in the areas of catalysis and corrosion. For example, the oxidation of a metal is faster when its area exposed to the oxidising medium increases. In general, it is seen that the rate of a heterogeneous reaction is directly proportional to the contact area between the reactants, S. Thus, in the rate law (2.17), these reactions are first order relative to S. ... 

The rate at which a reaction proceeds is governed by the principles of chemical kinetics, which is one of the major topics of this book. Chenucal kinetics allows us to understand how reaction rates depend on variables such as concentration, temperature, and pressure. Kinetics provides a basis for manipulating these variables to increase the rate of a desired reaction, and minimize the rates of undesired reactions. We will study kinetics first from a rather empirical standpoint, and lat from a more fundamental point of view, one that creates a link with the details of the reaction chenustry. Catalysis is an extremely important tool within the domain of chemical kinetics. For example, catalysts are required to ensure that blood clots form fast enough to fight serious blood loss. Approximately 90% of the chemical processes that are carried out industrially involve the use of some kind of catalyst in order to increase the rate(s) of the desired reaction(s). Unfortunately, the behavior of heterogeneous catalysts can be significantly and negatively influenced by the rates of heat and mass transfer to and from the sites in the catalyst whrae the reaction occurs. We will approach the interactions between catalytic kinetics and heat and mass transport conceptually and qualitatively at first, and then take them head-on later in the book. 

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