Homogeneous chemical reactions

It is assumed that a global chemical reaction (homogeneous or heterogeneous) and fluid flow take place within the tubular reactor with axial and radial dispersion of momentum, heat, and mass. This analysis is valid for any case however, we consider the physical and chemical properties of mixtures as ideal behavior. 

Chemical reaction (homogeneous, heterogeneous) Reaction overvoltage, tir... 

Cummings P T and Stell G 1984 Statistical mechanical models of chemical reactions II. Analytic solutions of the Percus-Yevick approximation for a model of homogeneous association Mol. Phys. 51 253... 

The nature of electrode processes can, of course, be more complex and also involve phase fonnation, homogeneous chemical reactions, adsorption or multiple electron transfer [1, 2, 3 and 4],... 

Double potential steps are usefiil to investigate the kinetics of homogeneous chemical reactions following electron transfer. In this case, after the first step—raising to a potential where the reduction of O to occurs under diffrision control—the potential is stepped back after a period i, to a value where tlie reduction of O is mass-transport controlled. The two transients can then be compared and tlie kinetic infomiation obtained by lookmg at the ratio of... 

Modelling plasma chemical systems is a complex task, because these system are far from thennodynamical equilibrium. A complete model includes the external electric circuit, the various physical volume and surface reactions, the space charges and the internal electric fields, the electron kinetics, the homogeneous chemical reactions in the plasma volume as well as the heterogeneous reactions at the walls or electrodes. These reactions are initiated primarily by the electrons. In most cases, plasma chemical reactors work with a flowing gas so that the flow conditions, laminar or turbulent, must be taken into account. As discussed before, the electron gas is not in thennodynamic equilibrium... 

Optically inactive starting materials can give optically active products only if they are treated with an optically active reagent or if the reaction is catalyzed by an optically active substance The best examples are found m biochemical processes Most bio chemical reactions are catalyzed by enzymes Enzymes are chiral and enantiomerically homogeneous they provide an asymmetric environment m which chemical reaction can take place Ordinarily enzyme catalyzed reactions occur with such a high level of stereo selectivity that one enantiomer of a substance is formed exclusively even when the sub strate is achiral The enzyme fumarase for example catalyzes hydration of the double bond of fumaric acid to malic acid m apples and other fruits Only the S enantiomer of malic acid is formed m this reaction... 

An increase in the time required to form a visible precipitate under conditions of low RSS is a consequence of both a slow rate of nucleation and a steady decrease in RSS as the precipitate forms. One solution to the latter problem is to chemically generate the precipitant in solution as the product of a slow chemical reaction. This maintains the RSS at an effectively constant level. The precipitate initially forms under conditions of low RSS, leading to the nucleation of a limited number of particles. As additional precipitant is created, nucleation is eventually superseded by particle growth. This process is called homogeneous precipitation. ... 

In the second method of homogeneous precipitation, the precipitant itself is generated by a chemical reaction. For example, Ba + can be homogeneously precipitated as BaS04 by hydrolyzing sulphamic acid to produce S04 . 

Sonochemistry can be roughly divided into categories based on the nature of the cavitation event homogeneous sonochemistry of hquids, heterogeneous sonochemistry of hquid—hquid or hquid—sohd systems, and sonocatalysis (which overlaps the first two) (12—15). In some cases, ultrasonic irradiation can increase reactivity by nearly a million-fold (16). Because cavitation can only occur in hquids, chemical reactions are not generaUy seen in the ultrasonic irradiation of sohds or sohd-gas systems. 

Mass-Transfer Coefficients with Chemical Reaction. Chemical reaction can occur ia any of the five regions shown ia Figure 3, ie, the bulk of each phase, the film ia each phase adjacent to the iaterface, and at the iaterface itself. Irreversible homogeneous reaction between the consolute component C and a reactant D ia phase B can be described as... 

Diluent Portion. The diluent portion of a flavor compound is the carrier for the color and the flavor, ie, the solvent for the flavor portion. It keeps the flavor homogenous, ie, keeps soflds in solution retards chemical reactions from occurring and regulates flavor strength, ie, the greater the amount of solvent, the weaker the flavor. 

Early ia the development of chemical reaction engineering, reactants and products were treated as existing ia single homogeneous phases or several discrete phases. The technology has evolved iato viewing reactants and products as residing ia interdependent environments, a most important factor for multiphase reactors which are the most common types encountered. 

Consider a closed PVT system, either homogeneous or heterogeneous, of uniform T and P, which is in thermal and mechanical equilibrium with its surroundings, but which is not initially at internal equilibrium with respect to mass transfer or with respect to chemical reaction. Changes occurring in the system are then irreversible, and must necessarily bring the system closer to an equihbrium state. The first and second laws written for the entire system are... 

Few mechanisms of liquid/liquid reactions have been established, although some related work such as on droplet sizes and power input has been done. Small contents of surface-ac tive and other impurities in reactants of commercial quality can distort a reac tor s predicted performance. Diffusivities in liquids are comparatively low, a factor of 10 less than in gases, so it is probable in most industrial examples that they are diffusion controllech One consequence is that L/L reactions may not be as temperature sensitive as ordinary chemical reactions, although the effec t of temperature rise on viscosity and droplet size can result in substantial rate increases. L/L reac tions will exhibit behavior of homogeneous reactions only when they are very slow, nonionic reactions being the most likely ones. On the whole, in the present state of the art, the design of L/L reactors must depend on scale-up from laboratoiy or pilot plant work. 

For many laboratoiy studies, a suitable reactor is a cell with independent agitation of each phase and an undisturbed interface of known area, like the item shown in Fig. 23-29d, Whether a rate process is controlled by a mass-transfer rate or a chemical reaction rate sometimes can be identified by simple parameters. When agitation is sufficient to produce a homogeneous dispersion and the rate varies with further increases of agitation, mass-transfer rates are likely to be significant. The effect of change in temperature is a major criterion-, a rise of 10°C (18°F) normally raises the rate of a chemical reaction by a factor of 2 to 3, but the mass-transfer rate by much less. There may be instances, however, where the combined effect on chemical equilibrium, diffusivity, viscosity, and surface tension also may give a comparable enhancement. 

The science of reaction kinetics between molecular species in a homogeneous gas phase was one of the earliest helds to be developed, and a quantitative calculation of tire rates of chemical reactions was considerably advatrced by the development of the collision theoty of gases. According to this approach the rate at which the classic reaction... 

If chemical reactions occur only over the catalyst and none on the walls or in the homogeneous fluid stream in the recycle loop, then conservation laws require that the two balances should be equal. 

A catalyst is defined as a substance that influences the rate or the direction of a chemical reaction without being consumed. Homogeneous catalytic processes are where the catalyst is dissolved in a liquid reaction medium. The varieties of chemical species that may act as homogeneous catalysts include anions, cations, neutral species, enzymes, and association complexes. In acid-base catalysis, one step in the reaction mechanism consists of a proton transfer between the catalyst and the substrate. The protonated reactant species or intermediate further reacts with either another species in the solution or by a decomposition process. Table 1-1 shows typical reactions of an acid-base catalysis. An example of an acid-base catalysis in solution is hydrolysis of esters by acids. 

The chemical reaction rate is generally a function of a reactant concentration and temperature. In the case of an exothermic reaction, unless the heat of reaction is removed, an increase in temperature may result in a runaway reaction. For most homogeneous reaction, the rate is increased by a factor of 2 or 3 for every 10°C rise in temperature. This is represented by... 

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... 

Emanuel, N.M. Knorre, D.C. Chemical Kinetics Homogeneous Reactions Wiley (Halsted Press) New York, 1973. 

The rate of a chemical reaction can be described in any of several different ways. The most commonly used definition involves the time rate of change in tlie amount of one of the components participating in tlie reaction tliis rate is usually based on some arbitrary factor related to tlie reacting system size or geometry, such as volume, mass, or interfacial area. Tlie definition shown in Eq. (4.6.7), wliich applies to homogeneous reactions, is a convenient one from an engineering point of view. 

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