Irreversible reactions order

For weU-defined reaction zones and irreversible, first-order reactions, the relative reaction and transport rates are expressed as the Hatta number, Ha (16). Ha equals (k- / l ) where k- = reaction rate constant, = molecular diffusivity of reactant, and k- = mass-transfer coefficient. Reaction... 

This development has been generalized. Results for zero- and second-order irreversible reactions are shown in Figure 10. Results are given elsewhere (48) for more complex kinetics, nonisothermal reactions, and particle shapes other than spheres. For nonspherical particles, the equivalent spherical radius, three times the particle volume/surface area, can be used for R to a good approximation. 

As discussed later, the reaction-enhancement factor ( ) will be large for all extremely fast pseudo-first-order reac tions and will be large tor extremely fast second-order irreversible reaction systems in which there is a sufficiently large excess of liquid-phase reagent. When the rate of an extremely fast second-order irreversible reaction system A -t-VB produc ts is limited by the availabihty of the liquid-phase reagent B, then the reac tion-enhancement factor may be estimated by the formula ( ) = 1 -t- B /VCj. In systems for which this formula is applicable, it can be shown that the interface concentration yj will be equal to zero whenever the ratio k yV/k B is less than or equal to unity. 

Figure 14-10 illustrates the gas-film and liquid-film concentration profiles one might find in an extremely fast (gas-phase mass-transfer limited) second-order irreversible reaction system. The solid curve for reagent B represents the case in which there is a large excess of bulk-liquid reagent B. The dashed curve in Fig. 14-10 represents the case in which the bulk concentration B is not sufficiently large to prevent the depletion of B near the liquid interface and for which the equation ( ) = I -t- B /vCj is applicable. 

Although the right-hand side of Eq. (14-60) remains valid even when chemical reactions are extremely slow, the mass-transfer driving force may become increasingly small, until finally c — Cj. For extremely slow first-order irreversible reactions, the following rate expression can be derived from Eq. (14-60) ... 

Estimation of for Irreversible Reactions Figure 14-14 illustrates the influence of either first- or second-order irreversible chemical reactions on the mass-transfer coefficient /cl as developed by Van Krevelen and Hoftyzer [Rec. Trav. Chim., 67, 563 (1948)] and as later refined by Periy and Pigford and by Brian et al. [Am. Inst. Chem. Eng. /., 7, 226(1961)]. 

An elementary explanation is given below for one of the cherished examples of Chemical Engineering the first order, monomolecular, irreversible reaction without change in mol numbers ... 

EMPIRICAL RATE EQUATIONS OF THE nth ORDER IRREVERSIBLE REACTIONS... 

Consider tlie ntli-order irreversible reaction of the form A —> products, (-r ) = kC, in a constant density single-stage CESTR. If n = 1, Equation 5-158 becomes... 

The material balance for the single CFSTR in terms of for the first order irreversible reaction is... 

Results of the intermediate conversions in a reactor train of CFSTRs involving the second order irreversible reaction kinetics A + B products... 

For the second order irreversible reaction, the selectivity of species R is... 

Consider a combination of CFSTR and plug flow systems as shown below for a first order irreversible reaction. 

Figure 5-38 shows plots of the dynamic response to changes in the inlet concentration of component A. The figure represents possible responses to an abrupt change in inlet concentration of an isothermal CFSTR with first order irreversible reaction. The first plot illustrates the situation where the reactor initially contains reactant at and... 

Fig ure 6-22. Temperature versus conversion for a first order irreversible reaction in an adiabatic continuous flow stirred tank reactor. 

This consists of two consecutive irreversible first-order (or pseudo-first-order) reactions. The differential rate equations are... 

Generalization of Scheme X to any number of consecutive irreversible first-order reactions is obviously possible, although the equations quickly become very cumbersome. However, Eqs. (3-42) and (3-44) reveal patterns in their form, and West-man and DeLury have developed a systematic symbolism that allows the equations to be written down without integration. 

A completely different dipolar cycloaddition model has been proposed39 in order to rationalize the stereochemical outcome of the addition of doubly deprotonated carboxylic acids to aldehydes, which is known as the Ivanov reaction. In the irreversible reaction of phenylacetic acid with 2,2-dimethylpropanal, metal chelation is completely unfavorable. Thus simple diastereoselectivity in favor of u f/-adducts is extremely low when chelating cations, e.g., Zn2 + or Mg- +, are used. Amazingly, the most naked dianions provide the highest anti/syn ratios as indicated by the results obtained with the potassium salt in the presence of a crown ether. 

The dissolved gas is removed from the liquid by an irreversible first-order reaction. 

Fig. 6. Film model for diffusion with simultaneous irreversible first-order chemical reaction [after Lightfoot (L5)].

Again for the case of the sparingly soluble gas whose absorption is accompanied by a simultaneous irreversible first-order reaction, Lightfoot (L5, L6) made the following assumptions ... 

Mass Transfer Accompanied by Irreversible First-Order Chemical Reaction... 

Fig. 10. Numerical solutions of the forced-convection mass-transfer equation for the case of irreversible first-order chemical reaction [after Johnson et al. (J4)] (Solid lines— rigid spheres dashed lines—circulating gas bubbles).

The following assumptions were made (1) The gas bubbles are evenly distributed throughout the liquid phase and have constant radius and composition (2) the concentration of the gas-liquid interface is constant and equal to C (3) no gross variations occur in liquid composition throughout the vessel and (4) the gas is sparingly soluble, and, in the case of a chemical reaction, it is removed by a first-order irreversible reaction with respect to the dissolving gas. 

In many applications of mass transfer the solute reacts with the medium as in the case, for example, of the absorption of carbon dioxide in an alkaline solution. The mass transfer rate then decreases in the direction of diffusion as a result of the reaction. Considering the unidirectional molecular diffusion of a component A through a distance Sy over area A. then, neglecting the effects of bulk flow, a material balance for an irreversible reaction of order n gives ... 

In a steady-state process, a gas is absorbed in a liquid with which it undergoes an irreversible reaction. The mass transfer process is governed by Fick s law, and the liquid is sufficiently deep for it to be regarded as effectively infinite in depth. On increasing the temperature, the concentration of reactant at the liquid surface CAi falls to 0.8 times its original value. The diffusivity is unchanged, but the reaction constant increases by a factor of 1.35. It is found that the mass transfer rate at the liquid surface falls to 0.83 times its original value. What is the order of the chemical reaction ... 

The treatment here is restricted to first-order irreversible reactions under steady-state conditions. Higher order reactions are considered by ARJS(30). 

Show that in steady-state diffusion through a film of liquid, accompanied by a first-order irreversible reaction, the concentration of solute in the film at depth r below the interface is given by ... 

A soluble gas is absorbed into a liquid with which it undergoes a second-order irreversible reaction. The process reaches a steady-state with the surface concentration of reacting material remaining constant at (.2ij and the depth of penetration of the reactant being small compared with the depth of liquid which can be regarded as infinite in extent. Derive the basic differential equation for the process and from this derive an expression for the concentration and mass transfer rate (moles per unit area and unit time) as a function of depth below the surface. Assume that mass transfer is by molecular diffusion. 

This definition for reaction order is directly meaningful only for irreversible or forward reactions that have rate expressions in the form of Equation (1.20). Components A, B,... are consumed by the reaction and have negative stoichiometric coefficients so that m = —va, n = —vb,. .. are positive. For elementary reactions, m and n must be integers of 2 or less and must sum to 2 or less. 

Section 5.1 shows how nonlinear regression analysis is used to model the temperature dependence of reaction rate constants. The functional form of the reaction rate was assumed e.g., St = kab for an irreversible, second-order reaction. The rate constant k was measured at several temperatures and was fit to an Arrhenius form, k = ko exp —Tact/T). This section expands the use of nonlinear regression to fit the compositional and temperature dependence of reaction rates. The general reaction is... 

The curves in Figure 7.2 plot the natural variable a t)laQ, versus time. Although this accurately portrays the goodness of fit, there is a classical technique for plotting batch data that is more sensitive to reaction order for irreversible Hth-order reactions. The reaction order is assumed and the experimental data are transformed to one of the following forms ... 

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