Thermodynamics affecting equilibrium

In this introductory chapter, we first consider what chemical kinetics and chemical reaction engineering (CRE) are about, and how they are interrelated. We then introduce some important aspects of kinetics and CRE, including the involvement of chemical stoichiometry, thermodynamics and equilibrium, and various other rate processes. Since the rate of reaction is of primary importance, we must pay attention to how it is defined, measured, and represented, and to the parameters that affect it. We also introduce some of the main considerations in reactor design, and parameters affecting reactor performance. These considerations lead to a plan of treatment for the following chapters. 

Chemical kinetics is concerned with the rate of reaction and factors affecting the rate, and chemical thermodynamics is concerned with the position of equilibrium and factors affecting equilibrium. 

Energy is an important component of most equilibrium systems. The input or output of energy in a system causes the temperature to change. Thus, the requirement that an equilibrium system be closed means that the temperature of the system must remain constant. In the next section, you will examine more closely the effects of thermodynamics on equilibrium systems. In particular, you will examine the factors that affect the amount of reactant and product in a reaction and the factors that determine whether or not a reaction is spontaneous. 

The heat of reaction for vinyl polymers affects the thermal stability of the polymer during extrusion, and the thermal stability is related to the ceiling temperature. The ceiling temperature is the temperature where the polymerization reaction equilibrium is shifted so that the monomer will not polymerize, or if kept at this temperature all the polymer will be converted back to monomer. From thermodynamics the equilibrium constant for any reaction is a function of the heat of reaction and the entropy of the reaction. For PS resin, the exothermic heat of reaction for polymerization is 70 kj/gmol, and the ceiling temperature is 310 °C. Ceiling temperatures for select polymers are shown in Table 2.5. 

The main reaction is the neutralization with ammonia, which is the major reactant. In case of thermodynamic equilibrium temperature and partial pressure of H2O, NHs and volatile acids (HNO3, HCl) it would be possible to describe the NHs-acid-ammonium salt system according to Gibbs phase rule, but in ambient air for the various meteorological factors affecting equilibrium this aim is not feasible. 

For 1-hexene Isomerization, lower temperatures slightly favor equilibrium conversion. Therefore, decreasing reaction temperature through the addition of a low T solvent such as CO2 is not thermodynamically unfavorable. However, the reaction may become klnetlcally limited. On the other hand, as seen from Figure 6, because temperature does not significantly affect equilibrium conversion. 

Dihydroxypteridine was expected to undergo hydration but, a priori, it was difficult to decide whether covalent hydration would occur across the 3,4- or the 7,8-position, or both. Kinetic and spectroscopic evidence now indicate that addition of water occurs much more rapidly across the 3,4-positions (and, hence, that the energy of activation must be less for this site), but the 7,8-water-adduct is thermodynamically the more stable. With time, the concentration of the species hydrated in the 3,4-position reaches a maximum (about 64% of the total concentration). Thereafter, it falls steadily and the concentration of the 7,8-adduct rises until, at equilibrium, the latter accounts for 92% of the total and the 3,4-adduct for only 7.6%. In 2,6-dihydroxy-4-methylpteridine, the methyl group drastically reduces the extent of water addition to the 3,4-position but does not significantly affect 7,8-addition, so that, spectroscopically, only a first-order conversion of anhydrous molecule into the 7,8-water-adduct is observed. ... 

The flow behavior of the polymer blends is quite complex, influenced by the equilibrium thermodynamic, dynamics of phase separation, morphology, and flow geometry [2]. The flow properties of a two phase blend of incompatible polymers are determined by the properties of the component, that is the continuous phase while adding a low-viscosity component to a high-viscosity component melt. As long as the latter forms a continuous phase, the viscosity of the blend remains high. As soon as the phase inversion [2] occurs, the viscosity of the blend falls sharply, even with a relatively low content of low-viscosity component. Therefore, the S-shaped concentration dependence of the viscosity of blend of incompatible polymers is an indication of phase inversion. The temperature dependence of the viscosity of blends is determined by the viscous flow of the dispersion medium, which is affected by the presence of a second component. 

The rate (or kinetics) and form of a corrosion reaction will be affected by a variety of factors associated with the metal and the metal surface (which can range from a planar outer surface to the surface within pits or fine cracks), and the environment. Thus heterogeneities in a metal (see Section 1.3) may have a marked effect on the kinetics of a reaction without affecting the thermodynamics of the system there is no reason to believe that a perfect single crystal of pure zinc completely free from lattic defects (a hypothetical concept) would not corrode when immersed in hydrochloric acid, but it would probably corrode at a significantly slower rate than polycrystalline pure zinc, although there is no thermodynamic difference between these two forms of zinc. Furthermore, although heavy metal impurities in zinc will affect the rate of reaction they cannot alter the final position of equilibrium. 

In some metal components it is possible to form oxides and carbides, and in others, especially those with a relatively wide solid solubility range, to partition the impurity between the solid and the liquid metal to provide an equilibrium distribution of impurities around the circuit. Typical examples of how thermodynamic affinities affect corrosion processes are seen in the way oxygen affects the corrosion behaviour of stainless steels in sodium and lithium environments. In sodium systems oxygen has a pronounced effect on corrosion behaviour whereas in liquid lithium it appears to have less of an effect compared with other impurities such as C and Nj. According to Casteels Li can also penetrate the surface of steels, react with interstitials to form low density compounds which then deform the surface by bulging. For further details see non-metal transfer. 

What Are the Key Ideas Equilibrium between two phases is reached when the rates of conversion between the two phases are the same in each direction. The rates are equal when the molar Gibbs free energy of the substance is the same in each phase and therefore there is no tendency to change in either direction. The same concepts apply to the dissolving of a solute. The presence of a solute alters the entropy of a solvent and consequently affects its thermodynamic properties. 

Why Do We Need to Know This Material The dynamic equilibrium toward which every chemical reaction tends is such an important aspect of the study of chemistry that four chapters of this book deal with it. We need to know the composition of a reaction mixture at equilibrium because it tells us how much product we can expect. To control the yield of a reaction, we need to understand the thermodynamic basis of equilibrium and how the position of equilibrium is affected by conditions such as temperature and pressure. The response of equilibria to changes in conditions has considerable economic and biological significance the regulation of chemical equilibrium affects the yields of products in industrial processes, and living cells struggle to avoid sinking into equilibrium. 

The overall change in free energy for the catalytic reaction equals that of the uncatalyzed reaction. Hence, the catalyst does not affect the equilibrium constant for the overall reaction of A -i- B to P. Thus, if a reaction is thermodynamically unfavorable, a catalyst cannot change this situation. A catalyst changes the kinetics but not the thermodynamics. 

Equilibrium data are thus necessary to estimate compositions of both extract and raffinate when the time of extraction is sufficiently long. Phase equilibria have been studied for many ternary systems and the data can be found in the open literature. However, the position of the envelope can be strongly affected by other components of the feed. Furthermore, the envelope line and the tie lines are a function of temperature. Therefore, they should be determined experimentally. The other shapes of the equilibrium line can be found in literature. Equilibria in multi-component mixtures cannot be presented in planar graphs. To deal with such systems lumping of consolutes has been done to describe the system as pseudo-ternary. This can, however, lead to considerable errors in the estimation of the composition of the phases. A more rigorous thermodynamic approach is needed to regress the experimental data on equilibria in these systems. 

All equilibrium constants in the present discussion are based on the concentration (not activity) scale. This is a perfectly acceptable thermodynamic scale, provided the ionic strength of the solvent medium is kept fked at a reference level (therefore, sufficiently higher than the concentration of the species assayed). This is known as the constant ionic medium thermodynamic state. Most modern results are determined at 25 °C in a 0.15 M KCl solution. If the ionic strength is changed, the ionization constant may be affected. For example, at 25 °C and 0.0 M ionic strength, the pXj of acetic acid is 4.76, but at ionic strength 0.15 M, the value is 4.55 [24]. 

A catalyst cannot change the ultimate equilibrium point set by thermodynamics, but it can affect the rate at which this point is approached. However, it can facilitate approach to equilibrium with respect to a desired reaction while not influencing the rates of other less desirable reactions. In optimizing yields of desired products, chemical engineers are very concerned with the selectivity or specificity of a catalyst. For commercial applications, selectivity is often more important than activity per se. 

The thermodynamic effects of electric fields and are well known. Application of an electric field to a solution can affect the chemical equilibrium. For example, in Eq. (18) where C has a large dipole moment and B has a small dipole moment the equilibrium is shifted toward C under the action of an electric field. 

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