Temperature chemical equilibrium dependence

The chemical equilibrium assumption often results in modeling predictions similar to those obtained assuming infinitely fast reaction, at least for overall aspects of practical systems such as combustion. However, the increased computational complexity of the chemical equilibrium approach is often justified, since the restrictions that the equilibrium constraint places on the reaction system are accounted for. The fractional conversion of reactants to products at chemical equilibrium typically depends strongly on temperature. For an exothermic reaction system, complete conversion to products is favored thermodynamically at low temperatures, while at high temperatures the equilibrium may shift toward reactants. The restrictions that equilibrium place on the reaction system are obviously not accounted for by the fast chemistry approximation. 

For any application, it is particularly important to consider on which variables the chemical equilibrium constant depends. For gas-phase reactions, equations (4.14) and (4.15) are generally applied, where (Tp ) is a function of the temperature alone. For liquid-phase reactions, equations (4.12) and (4.13) are used in most cases. As the influence of pressure on (Tp) can generally be neglected, again only a function of temperature has to be known. 

Fluctuations of observables from their average values, unless the observables are constants of motion, are especially important, since they are related to the response fiinctions of the system. For example, the constant volume specific heat of a fluid is a response function related to the fluctuations in the energy of a system at constant N, V and T, where A is the number of particles in a volume V at temperature T. Similarly, fluctuations in the number density (p = N/V) of an open system at constant p, V and T, where p is the chemical potential, are related to the isothemial compressibility iCp which is another response fiinction. Temperature-dependent fluctuations characterize the dynamic equilibrium of themiodynamic systems, in contrast to the equilibrium of purely mechanical bodies in which fluctuations are absent. 

Clausius-Clapeyron equation An equation expressing the temperature dependence of vapor pressure ln(P2/Pi) = AHvapCl/Tj - 1/T2)/R, 230,303-305 Claussen, Walter, 66 Cobalt, 410-411 Cobalt (II) chloride, 66 Coefficient A number preceding a formula in a chemical equation, 61 Coefficient rule Rule which states that when the coefficients of a chemical equation are multiplied by a number n, the equilibrium constant is raised to the nth power, 327... 

A catalyst speeds up both the forward and the reverse reactions by the same amount. Therefore, the dynamic equilibrium is unaffected. The thermodynamic justification of this observation is based on the fact that the equilibrium constant depends only on the temperature and the value of AGr°. A standard Gibbs free energy of reaction depends only on the identities of the reactants and products and is independent of the rate of the reaction or the presence of any substances that do not appear in the overall chemical equation for the reaction. 

The concentrations of base-metals (Cu, Fe, Pb, and Zn) in hydrothermal solution in equilibrium with sulfides (chalcopyrite, pyrite, galena and sphalerite) depend on several variables such as pH, ntQx- concentration, temperature, /WH2S, and fo2- The relation between the concentrations and these variables can be derived based on the chemical equilibrium for the following reactions. 

Chemical equilibrium depends on temperature as described by the van t Hoff equation... 

Here K is the thermodynamic chemical equilibrium constant. If AH is constant, direct integration yields an explicit expression. If AH is a function of temperature, as described in Sec. 1.3.3, then its dependancy on Cp can be easily included and integration is again straight forward. A calculation with varying AH and Cp being functions of temperature is given in the simulation example REVTEMP. 

Here, the sign of equality (=) has been replaced by the double oppositely directed arrows (s=) called a sign of reversibility. Such a reaction is called a reversible reaction. The reversibility of reactions can be detected when both the forward and the reverse reactions occur to a noticeable extent. Generally, such reactions are described as reversible reactions. The most important criterion of a reaction of this type is that none of the reactants will become exhausted. When the reaction is allowed to take place in a closed system from where none of the substances involved in the reaction can escape, one obtains a mixture of the reactants and the products in the reaction vessel. Every reversible reaction, depending on its nature, will after some time reach a stage when the reactants and the products coexist in a state of balance, and their amounts will remain unaltered for unlimited time. Such a state of a chemical reaction is called chemical equilibrium, and the point of such an equilibrium varies only with temperature. 

When a solid acts as a catalyst for a reaction, reactant molecules are converted into product molecules at the fluid-solid interface. To use the catalyst efficiently, we must ensure that fresh reactant molecules are supplied and product molecules removed continuously. Otherwise, chemical equilibrium would be established in the fluid adjacent to the surface, and the desired reaction would proceed no further. Ordinarily, supply and removal of the species in question depend on two physical rate processes in series. These processes involve mass transfer between the bulk fluid and the external surface of the catalyst and transport from the external surface to the internal surfaces of the solid. The concept of effectiveness factors developed in Section 12.3 permits one to average the reaction rate over the pore structure to obtain an expression for the rate in terms of the reactant concentrations and temperatures prevailing at the exterior surface of the catalyst. In some instances, the external surface concentrations do not differ appreciably from those prevailing in the bulk fluid. In other cases, a significant concentration difference arises as a consequence of physical limitations on the rate at which reactant molecules can be transported from the bulk fluid to the exterior surface of the catalyst particle. Here, we discuss... 

Calculations Equilibrium Dissolved gases Rates of reaction Chemical potential and AG with the extent of reaction Henry s Law and the pH of the oceans Temperature dependence of chemistry and the analysis of chemical networks in prebiotic environments... 

Essentially, all reactions that require the formation of a chemical bond with an activation energy of around 100 kJ mol-1 are frozen out at the surface of Titan but are considerably faster in the stratosphere, although still rather slow compared with the rates of reaction at 298 K. Chemistry in the atmosphere of Titan will proceed slowly for neutral reactions but faster for ion-molecule reactions and radical-neutral reactions, both of which have low activation barriers. The Arrhenius equation provides the temperature dependence of rates of reactions but we also need to consider the effect of cold temperatures on thermodynamics and in particular equilibrium. 

The l3C NMR spectrum of the C4H7+ cation in superacid solution shows a single peak for the three methylene carbon atoms (72) This equivalence can be explained by a nonclassical single symmetric (three-fold) structure. However, studies on the solvolysis of labeled cyclopropylcarbinyl derivatives suggest a degenerate equilibrium among carbocations with lower symmetry, instead of the three-fold symmetrical species (13). A small temperature dependence of the l3C chemical shifts indicated the presence of two carbocations, one of them in small amounts but still in equilibrium with the major species (13). This conclusion was supported by isotope perturbation experiments performed by Saunders and Siehl (14). The classical cyclopropylcarbinyl cation and the nonclassical bicyclobutonium cation were considered as the most likely species participating in this equilibrium. 

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