Exothermic process equilibrium constant

Reaction (2) is an outer-sphere exothermic process (AE° is about —0.4 V) and therefore, the equilibrium of this reaction is completely shifted to the right, i.e., the reoxidation of reduced cytochrome c by dioxygen is impossible. However, the rate constant for Reaction (2) (2.6 + O.lxlO5 1 moR1 s 1) is unexpectedly low for the exothermic one-electron transfer... 

One of the issues of the industrial process design is related to the heat released by this reaction. A temperature rise will decrease the acetic acid yield, not only because the equilibrium constant becomes lower (the reaction is exothermic see section 2.9) but also because it will reduce the enzyme activity. It is therefore important to keep the reaction temperature within a certain range, for instance, by using a heat exchanger. However, to design this device we need to know the reaction enthalpy under the experimental conditions, and this quantity cannot be easily found in the chemical literature. 

In Figure 2.4, data for the equilibrium constants of esterification/hydrolysis and transesterification/glycolysis from different publications [21-24] are compared. In addition, the equilibrium constant data for the reaction TPA + 2EG BHET + 2W, as calculated by a Gibbs reactor model included in the commercial process simulator Chemcad, are also shown. The equilibrium constants for the respective reactions show the same tendency, although the correspondence is not as good as required for a reliable rigorous modelling of the esterification process. The thermodynamic data, as well as the dependency of the equilibrium constants on temperature, indicate that the esterification reactions of the model compounds are moderately endothermic. The transesterification process is a moderately exothermic reaction. 

Explain why the following statements about elementary reactions are wrong, (a) The equilibrium constant for a reaction equals the ratio of the forward and reverse rates, (b) For an exothermic process, the rates of the forward and reverse reactions are affected in the same way by a rise in temperature. 

The thermodynamics and kinetics of the thermal equilibrium between previtamin D3 and vitamin D3 have been studied (34,35). The isomerization of previtamin D3 to vitamin 63 is an exothermic first order reaction. The vitamin D3/previtamin D3 equilibrium ratio depends on the temperature and can be calculated from the appropriate equilibrium and kinetic constants reported by Hanewald et al. (36). The rate constants for the equilibrium have been shown to be independent of the nature of the solvent, of acidic or basic catalysis and of factors known to affect free radical process (37,38). The percentages of vitamin D3 in equilibrium with previtamin D3 ranges from 98% at -20° to 78% at 80°. Thus, when vitamin D3 is stored in the cold, the equilibrium constant hinders the conversion to previtamin D3. 

The process is subjected to a number of disturbances, and the control structure handles all of them quite effectively. Dynamic responses to changes in the setpoint of the temperature controller in the first reactor are shown in Figure 6.109. At 0.1 h, the setpoint is increased from 245 to 255°C. At 3 h, it is decreased to 235°C. Decreasing the temperature in the first reactor results in an increase in throughput. The synthesis gas feedrate, the product rate, and the vent rate all increase. The opposite occurs when the temperature is increased. This indicates that the reaction is equilibrium-limited, not kinetically limited. Decreasing temperature increases the equilibrium constant of exothermic reactions. 

Le Chatelier s principle predicts that when heat is added at constant pressure to a system at equilibrium, the reaction will shift in the direction that absorbs heat until a new equilibrium is established. For an endothermic process, the reaction will shift to the right towards product formation. For an exothermic process, the reaction will shift to the left towards reactant formation. If you understand the application of Le Chatelier s principle to concentration changes then writing "heat" on the appropriate side of the equation will help you understand its application to changes in temperature. 

From Eqn. (14) it follows that with an exothermic reaction - and this is the case for most reactions in reactive absorption processes - decreases with increasing temperature. The electrolyte solution chemistry involves a variety of chemical reactions in the liquid phase, for example, complete dissociation of strong electrolytes, partial dissociation of weak electrolytes, reactions among ionic species, and complex ion formation. These reactions occur very rapidly, and hence, chemical equilibrium conditions are often assumed. Therefore, for electrolyte systems, chemical equilibrium calculations are of special importance. Concentration or activity-based reaction equilibrium constants as functions of temperature can be found in the literature [50]. 

Thermodynamically the insertion of an alkene into a metal-hydride bond is much more favourable than the insertion of carbon monoxide into a metal-methyl bond. The latter reaction is more or less thermoneutral and the equilibrium constant is near unity under standard conditions. The metal-hydride bond is stronger than a metal-carbon bond and the insertion of carbon monoxide into a metal hydride is thermodynamically most often uphill. Insertion of alkenes is also a reversible process, but slightly more favourable than CO insertion. Formation of new CT bonds at the cost of the loss of the ji bond of the alkene during alkene hydrogenation etc., makes the overall processes of alkenes thermodynamically exothermic, especially for early transition metals. 

However, this reaction is very slow in the absence of a catalyst. One of the mysteries during early research on air pollution was how the sulfur dioxide produced from the combustion of sulfur-containing fuels is so rapidly converted to sulfur trioxide in the atmosphere. It is now known that dust and other particles can act as heterogeneous catalysts for this process (see Section 15.9). In the preparation of sulfur trioxide for the manufacture of sulfuric acid, either platinum metal or vanadium(V) oxide (V205) is used as a catalyst, and the reaction is carried out at approximately 500°C, even though this temperature decreases the value of the equilibrium constant for this exothermic reaction. 

Increasing temperature decreases the time needed to reach equilibrium as well as the amount of analyte extracted. Extraction recoveries at a constant temperature increase with exposure time and reach a plateau when equilibrium is established. This can be explained because the rate-limited step, the transport of analytes from the liquid to the headspace, is speeded up. The decrease in the extracted quantities of analytes onto the fiber (specially the less volatile) with increasing temperature is a result of the exothermic process of adsorption. 

Operating at higher temperatures increases the reaction rate but reduces K (T) enormously because the reaction is exothermic and the variation of equilibrium constant with temperature is similar to that shown in Fig. 15.6. (For the Haber-Bosch process, = 60 moH dm at 227°C and at 0.02 mol dm at 527°C.)... 

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