Reaction equilibrium multiple reactions

Most processes are catalyzed where catalysts for the reaction are known. The choice of catalyst is crucially important. Catalysts increase the rate of reaction but are unchanged in quantity and chemical composition at the end of the reaction. If the catalyst is used to accelerate a reversible reaction, it does not by itself alter the position of the equilibrium. When systems of multiple reactions are involved, the catalyst may have different effects on the rates of the different reactions. This allows catalysts to be developed which increase the rate of the desired reactions relative to the undesired reactions. Hence the choice of catalyst can have a major influence on selectivity. 

For multiple reactions in which the byproduct is formed in series, the selectivity decreases as conversion increases. In this case, lower conversion than that for single reactions is expected to be appropriate. Again, the best guess at this stage is to set the conversion to 50 percent for irreversible reactions or to 50 percent of the equilibrium conversion for reversible reactions. 

The hydrogen concentration contours for 50 atm and 700°K (Figure 8) indicate that there is appreciable unreacted hydrogen after equilibrium is reached. It is clear that multiple reaction stages are required to approach pure methane. 

Equilibrium Compositions for Multiple Reactions. When there are two or more independent reactions. Equation (7.29) is written for each reaction ... 

In the preceding chapter, the choice of reactor type was made on the basis of the most appropriate concentration profile as the reaction progressed, in order to minimize reactor volume for single reactions or maximize selectivity (or yield) for multiple reactions for a given conversion. However, there are still important effects regarding reaction conditions to be considered. Before considering reaction conditions, some basic principles of chemical equilibrium need to be reviewed. 

The selection of reactor pressure for vapor-phase reversible reactions depends on whether there is a decrease or an increase in the number of moles. The value of AN in Equation 6.25 dictates whether the equilibrium conversion will increase or decrease with increasing pressure. If AN is negative, the equilibrium conversion will increase with increasing pressure. If AN is positive, it will decrease. The choice of pressure must also take account of whether the system involves multiple reactions. 

It is noteworthy that all these reactions are reversible, but under reducing conditions the equilibrium shifts to the right-hand side, and under oxidizing conditions it shifts to the left-hand side. For all resulting binuclear ions at rather low concentration in solutions, reactions take place, accompanied by the rupture of the M-M bond and the formation of unstable mononuclear complexes, which are readily oxidized even by the solvent. At high concentrations of binuclear ions cycloaddition reactions of multiple M-M bonds (these reactions are considered in section 3.5) occur to form stable, under the given conditions, polynuclear clusters. 

The treatment of chemical reaction equilibria outlined above can be generalized to cover the situation where multiple reactions occur simultaneously. In theory one can take all conceivable reactions into account in computing the composition of a gas mixture at equilibrium. However, because of kinetic limitations on the rate of approach to equilibrium of certain reactions, one can treat many systems as if equilibrium is achieved in some reactions, but not in others. In many cases reactions that are thermodynamically possible do not, in fact, occur at appreciable rates. 

Although we have indicated some applications of thermodynamics to biological systems, more extensive discussions are available [6]. The study of equilibrium involving multiple reactions in multiphase systems and the estimation of their thermodynamic properties are now easier as a result of the development of computers and appropriate algorithms [7]. 

In this chapter we deal with single reactions. These are reactions whose progress can be described and followed adequately by using one and only one rate expression coupled with the necessary stoichiometric and equilibrium expressions. For such reactions product distribution is fixed hence, the important factor in comparing designs is the reactor size. We consider in turn the size comparison of various single and multiple ideal reactor systems. Then we introduce the recycle reactor and develop its performance equations. Finally, we treat a rather unique type of reaction, the autocatalytic reaction, and show how to apply our findings to it. 

Students may have seen the acetaldehyde decomposition reaction system described as an example of the application of the pseudo steady state (PSS), which is usually covered in courses in chemical kinetics. We dealt with this assumption in Chapter 4 (along with the equilibrium step assumption) in the section on approximate methods for handling multiple reaction systems. In this approximation one tries to approximate a set of reactions by a simpler single reaction by invoking the pseudo steady state on suitable intermediate species. 

In catalytic distillation the temperature also varies with position in the column, and this will change the reaction rates and selectivities as well as the equilibrium compositions. Temperature variations between stages and vapor pressures of reactants and products can be exploited in designing for multiple-reaction processes to achieve a high selectivity to a desired product with essentially no unwanted products. 

Equation (2.38) has a first-order sink and a zero-order source, which meets our criteria for an analytical solution to the diffusion equation. Ce is the concentration of C at equilibrium for the reaction. This technique of assuming that multiple reactions are zero-order and first-order reactions will be utilized in Example 2.9. 

S. Ung and M. F. Doherty, Calculation of residue curve maps for mixtures with multiple equilibrium chemical reactions. Ind. Engng. Chem. Res.,... 

Example 4.8 Chemical reactions and reacting flows The extension of the theory of linear nonequilibrium thermodynamics to nonlinear systems can describe systems far from equilibrium, such as open chemical reactions. Some chemical reactions may include multiple stationary states, periodic and nonperiodic oscillations, chemical waves, and spatial patterns. The determination of entropy of stationary states in a continuously stirred tank reactor may provide insight into the thermodynamics of open nonlinear systems and the optimum operating conditions of multiphase combustion. These conditions may be achieved by minimizing entropy production and the lost available work, which may lead to the maximum net energy output per unit mass of the flow at the reactor exit. 

This chapter, after introducing the equilibrium constant, discusses briefly the rate of entropy production in chemical reactions and coupling aspects of multiple reactions. Enzyme kinetics is also summarized. 

The screen for each chemical kinetic calculation simultaneously displays a variety of characterizations in multiple windows and allows analysis of time/temperature-dependent species and reaction information including species concentrations, species steady-state analysis, individual reaction rates, net production/destruction rates, reaction equilibrium analysis and the temperature/time history of the system. The interactive user-sorting of the species and reaction information from the numerical simulations is mouse/cursor driven. An additional feature also allows interactive analysis and identification of dependent and independent species and reaction pathways, on-line reaction network analysis and pathway/flowchart construe-... 

This model represents the most frequently used description of chemical reaction equilibrium and should be familiar to most chemical engineering students. However, for multicomponent mixtures in which multiple reactions may take place, this type of non-linear problems may be cumbersome to solve numerically. One important obstacle is that the non-linear equilibrium constant definitions may give rise to multiple solutions, hence we have to identify which of them are the physical solutions. The stoichiometric formulation might thus be inconvenient for mixtures containing just a few species for which only a few reactions are taking place. 

In this chapter, you have derived the equations governing chemical reaction equilibrium and seen how the key parameters can be estimated using thermodynamics. You have solved the resulting problems using Excel, MATLAB, and Aspen Plus. You also learned to solve multiple equations using MATLAB when there are several reactions in equilibrium. 

Identification and quantification of the desired reaction conditions, particularly temperature and concentration, are necessary to evaluate what may happen if these conditions are not met. This is particularly true where equilibrium considerations are a significant factor in a rate determining step between or among competing reactions. Where multiple products are possible, temperature variations will often significantly alter the ratios of these products. If one of these is unstable or more toxic, this could lead to more stringent temperature control requirements in the process and equipment design. 

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