Chemical reaction equilibrium conversion

When setting the conditions in chemical reactors, equilibrium conversion will be a major consideration for reversible reactions. The equilibrium constant Ka is only a function of temperature, and Equation 6.19 provides the quantitative relationship. However, pressure change and change in concentration can be used to shift the equilibrium by changing the activities in the equilibrium constant, as will be seen later. 

Hougen- Watson Models for Cases where Adsorption and Desorption Processes are the Rate Limiting Steps. When surface reaction processes are very rapid, the overall conversion rate may be limited by the rate at which adsorption of reactants or desorption of products takes place. Usually only one of the many species in a reaction mixture will not be in adsorptive equilibrium. This generalization will be taken as a basis for developing the expressions for overall conversion rates that apply when adsorption or desorption processes are rate limiting. In this treatment we will assume that chemical reaction equilibrium exists between various adsorbed species on the catalyst surface, even though reaction equilibrium will not prevail in the fluid phase. 

Calculation of equilibrium conversions is based on the fundamental equations of chemical-reaction equilibrium, which in application require data for the standard Gibbs energy of reaction. The basic equations are developed in Secs. 15.1 through 15.4. These provide the relationship between the standard Gibbs energy change of reaction and the equilibrium constant. Evaluation of the equilibrium constant from thermodynamic data is considered in Sec. 15.5. Application of this information to the calculation of equilibrium conversions for single reactions is taken up in Sec. 15.7. In Sec. 15.8, the phase role is reconsidered finally, multireaction equilibrium is treated in Sec. I5.9.t... 

Carnot s equations, 146-147 Carnot s theorem, 142-143 Chemical potential, 298, 302, 303 as equilibrium criterion, 298-299, 503 for ideal gas, 302 for ideal solution, 303 Chemical reaction equilibrium constant for, 504-516 equilibrium conversion of, 518-528, 533-542 heat effects of, 116-133 reaction coordinate for, 497-501 reversible, 41-42, 505-507 standard property changes for, 125, 505 stoichiometry, 497-501... 

This chapter shows how to solve problems involving chemical reaction equihbrium. The chemical reaction equilibrium gives the upper limit for the conversion, so knowing the equilibrium conversion is the first step in analyzing a process. The second question, what the rate of reaction is, can then be answered to decide the volume of the reactor. This second question, using kinetics, is treated in Chapter 8. Chemical reaction equilibrium leads to one or more nonlinear algebraic equations which must be solved simultaneously, and such problems are described in this chapter. 

In applying Eqs. (1.3-40) and (1.3-41). one reeks expressions for the apparent quantities Z and i-,. To do this, one must propose a reaction scheme this provides relationships for n ln aed y-ly- in terms of equilibrium conversions. One must also assume an expression for 2. which in him implies an expression for the l The true fugacity coefficients 0, , when incorporated into the crirerin for chemical-reaction equilibrium for the uue mixture, permit determination of (he equilibrium conversions, and hence, fienlly. via Eqs. (1.3-40) and (1.3-41). expressions for Z and , as functions of T. P, and the set of appnrear compositions y J. 

When striving for high reactor conversions, it may be necessary to consider the reverse reaction even when the reaction is considered to be irreversible. This is the case for the hydrodealkylation of toluene. A rate equation for the reverse reaction can be derived from the rate equation for the forward reaction, given by Eq. (8.2), by assuming that the two rate equations are consistent with the chemical-reaction equilibrium constant. Assume that the gas reacting mixture is ideal at the high temperature of the reaction. Then, the chemical equilibrium constant can be expressed in terms of concentrations and equated to the ratio of the rate constants by ... 

As shown in Section 8.3, this reaction, while not completely irreversible at typical reactor operating conditions, has a chemical-reaction equilibrium constant high enough to give conversions greater than 99%. When the main reaction is carried out thermally, in the absence of a catalyst, it is accompanied by the following side reaction that produces the byproduct, biphenyl ... 

Our objective in this Chapter is to demonstrate how these equations - with their rather abstract quantities - can be used in determining the equilibrium conversion of a reacting system, which - as outlined in the Introduction - represents the contribution of thermodynamics to the application of chemical reaction equilibrium in the Chemical and Petroleum Industries. More specifically our objective is to examine how ... 

Here the exchange rate TZq (the rate of the forward and back reactions at equilibrium) appears as the relevant permeabihty parameter for the reaction in the linear regime. However, the limitation introduced, viz. ArG free standard enthalpy of reaction can certainly reach MJ in its order of magnitude. Equation (6.21) is only obeyed in the immediate neighbourhood of the equilibrium and is, thus, of little utihly for typical chemical reactions. If conversely I ArG I RT then, depending on the sign of ArG, K is determined by the forward reaction (kNA) or the back reaction (kNe) alone and the explicit dependence on... 

Similarly, chemical reaction equilibrium represents a dynamic process on the molecular scale. Macroscopically, a reaction can proceed in the forward direction from reactants to products or in the reverse direction from products to reactants. A given reaction is said to be at chemical reaction equilibrium when there is no net reaction in either direction. However, again there is a dynamic process on a molecular scale. Reactant molecules will react to form products at the same rate that the product molecules form reactants. If we followed an individual molecule, it might indeed react. However, for each molecule that reacts in the forward direction, another molecule will be reacting in the reverse direction. On the other hand, if an excess of reactants is present, there will be a net macroscopic reaction in ihe forward direction, since more individual molecules will react in this direction than in the reverse direction. Reaction will occur until equilibrium is reached and there is no more tendency to react on a macroscopic scale. Conversely, if an excess of products is present, macroscopic reaction will occur in the reverse direction until the same equilibrium state is reached. 

Figure 2,9 Various measures can be taken to increase equilibrium conversion in reversible reactions. (From Smith and Petela, The Chemical Engineer, Dec. 17, 1991 reproduced by permission of the Institution of Chemical Engineers.)...

A catalyst is a material that accelerates a reaction rate towards thennodynamic equilibrium conversion without itself being consumed in the reaction. Reactions occur on catalysts at particular sites, called active sites , which may have different electronic and geometric structures than neighbouring sites. Catalytic reactions are at the heart of many chemical industries, and account for a large fraction of worldwide chemical production. Research into fiindamental aspects of catalytic reactions has a strong economic motivating factor a better understanding of the catalytic process... 

Aside from merely calculational difficulties, the existence of a low-temperature rate-constant limit poses a conceptual problem. In fact, one may question the actual meaning of the rate constant at r = 0, when the TST conditions listed above are not fulfilled. If the potential has a double-well shape, then quantum mechanics predicts coherent oscillations of probability between the wells, rather than the exponential decay towards equilibrium. These oscillations are associated with tunneling splitting measured spectroscopically, not with a chemical conversion. Therefore, a simple one-dimensional system has no rate constant at T = 0, unless it is a metastable potential without a bound final state. In practice, however, there are exchange chemical reactions, characterized by symmetric, or nearly symmetric double-well potentials, in which the rate constant is measured. To account for this, one has to admit the existence of some external mechanism whose role is to destroy the phase coherence. It is here that the need to introduce a heat bath arises. 

Chain uncoiling, and the converse process of coiling, is conveniently considered as a unimolecular chemical reaction. It is assumed that the rate of uncoiling at any time after application of a stress is proportional to the molecules still coiled. The deformation Dhe(0 at tinie t after application of stress can be shown to be related to the equilibrium deformation Dhe( ) by the equation... 

Some chemical reactions are reversible and, no matter how fast a reaction takes place, it cannot proceed beyond the point of chemical equilibrium in the reaction mixture at the specified temperature and pressure. Thus, for any given conditions, the principle of chemical equilibrium expressed as the equilibrium constant, K, determines how far the reaction can proceed if adequate time is allowed for equilibrium to be attained. Alternatively, the principle of chemical kinetics determines at what rate the reaction will proceed towards attaining the maximum. If the equilibrium constant K is very large, for all practical purposes the reaction is irreversible. In the case where a reaction is irreversible, it is unnecessary to calculate the equilibrium constant and check the position of equilibrium when high conversions are needed. 

Fig ure 6-12. Profiles of equilibrium conversion Xg versus temperature T for ammonia synthesis. (Source Schmidt, L. D., The Engineering of Chemical Reactions, Oxford University Press, New York, 1998.)... 

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... 

One difficulty Haber faced is that the reactions used to produce compounds from nitrogen do not go to completion, but appear to stop after only some of the reactants have been used up. At this point the mixture of reactants and products has reached chemical equilibrium, the stage in a chemical reaction when there is no further tendency for the composition of the reaction mixture—the concentrations or partial pressures of the reactants and products—to change. To achieve the greatest conversion of nitrogen into its compounds, Haber had to understand how a reaction approaches and eventually reaches equilibrium and then use that... 

Despite this much-discussed theoretical background, the number of concrete studies comparing historical ideas and students conceptions is fairly low in chemistiy education. Furthermore, most studies cited deal with isolated topics. Systematic overviews concerning basic ideas like micro-macro thinking, chemical reaction, the particulate nature of matter, energy conversions etc. are mostly not available, except for van Driel et al. (1998) and the case of the chemical equilibrium. 

Membranes in catalysis can be used to improve selectivity and conversion of a chemical reaction, improve stability and lifetime of the catalyst, and improve the safety of operation. The most well-known example is in situ removal of products of an equilibrium-limited reaction. However, many more ways of application of a membrane can be thought of [1-3], such as using the membrane as a reactant distributor to control the reactant concentration levels in the reactor, or performing catalysis inside the membrane and having control over reactant feed and product removal. 

While all chemical reactions are to some extent reversible, at equilibrium the overall concentrations of reactants and products remain constant. At equihbrium, the rate of conversion of substrates to products therefore equals the rate at which products are converted to substrates. 

In order to obtain a definite breakthrough of current across an electrode, a potential in excess of its equilibrium potential must be applied any such excess potential is called an overpotential. If it concerns an ideal polarizable electrode, i.e., an electrode whose surface acts as an ideal catalyst in the electrolytic process, then the overpotential can be considered merely as a diffusion overpotential (nD) and yields (cf., Section 3.1) a real diffusion current. Often, however, the electrode surface is not ideal, which means that the purely chemical reaction concerned has a free enthalpy barrier especially at low current density, where the ion diffusion control of the electrolytic conversion becomes less pronounced, the thermal activation energy (AG°) plays an appreciable role, so that, once the activated complex is reached at the maximum of the enthalpy barrier, only a fraction a (the transfer coefficient) of the electrical energy difference nF(E ml - E ) = nFtjt is used for conversion. 

Keywords chemical energy conversion energy storage chemical heat pump separation hydrogen production reaction equilibrium... 

Chemical heat pump uses chemical reaction for thermal energy storage and conversion. The heat pump operation is based on reaction equilibrium relationship, and has two operation modes. Figure 221 shows equilibrium relationship of chemical heat pump cycle for Mg0/H20 system at (a) heat amplification and cooling mode and (b) heat transformation mode [26], Figure 222 shows... 

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