Gibbs energy chemical equilibrium

Partial molar Gibbs energies (chemical potentials) can be obtained by measurement of the equilibrium pressure of a gas phase above a condensed phase, for example above a compound or a solution of given composition. 

In this introductory chapter, we define chemical equilibrium. The Gibbs energy is the energy that is most useful to us, because processes at constant T and p (conditions that are easily established) have dG as a spontaneity condition. Therefore, we relate the idea of chemical equilibrium to the Gibbs energy. Chemical reactions go only so far toward completion, and we define extent as a means of expressing how far a reaction proceeds as pure reactants proceed toward products. We use extent to help define chemical equilibrium. 

Gibbs energy and equilibrium constant of a chemical reaction depends on the local environment. For example, the equilibrium constant for protolytic reaction... 

The most important themiodynamic property of a substance is the standard Gibbs energy of fomiation as a fimetion of temperature as this infomiation allows equilibrium constants for chemical reactions to be calculated. The standard Gibbs energy of fomiation A G° at 298.15 K can be derived from the enthalpy of fomiation AfT° at 298.15 K and the standard entropy AS° at 298.15 K from... 

Quantity K is the chemical reaction equilibrium constant for reactionyj and AG° is the corresponding standard Gibbs energy change of reaction (eq. 237). Although called a constant, fC is a function of T, but only of T. 

The chemical potential pi plays a vital role in both phase and chemical-reaction equilibria. However, the chemical potential exhibits certain unfortunate characteristics which discourage its use in the solution of practical problems. The Gibbs energy, and hence pi, is defined in relation to the internal energy and entropy, both primitive quantities for which absolute values are unknown. Moreover, pi approaches negative infinity when either P or Xi approaches zero. While these characteristics do not preclude the use of chemical potentials, the application of equilibrium criteria is facilitated by introduction of the fugacity, a quantity that takes the place of p. but which does not exhibit its less desirable characteristics. 

The standard Gibbs-energy change of reaction AG° is used in the calculation of equilibrium compositions. The standard heat of reaclion AH° is used in the calculation of the heat effects of chemical reaction, and the standard heat-capacity change of reaction is used for extrapolating AH° and AG° with T. Numerical values for AH° and AG° are computed from tabulated formation data, and AC° is determined from empirical expressions for the T dependence of the C° (see, e.g., Eq. [4-142]). 

When the kinetics are unknown, still-useful information can be obtained by finding equilibrium compositions at fixed temperature or adiabatically, or at some specified approach to the adiabatic temperature, say within 25°C (45°F) of it. Such calculations require only an input of the components of the feed and produc ts and their thermodynamic properties, not their stoichiometric relations, and are based on Gibbs energy minimization. Computer programs appear, for instance, in Smith and Missen Chemical Reaction Equilibrium Analysis Theory and Algorithms, Wiley, 1982), but the problem often is laborious enough to warrant use of one of the several available commercial services and their data banks. Several simpler cases with specified stoichiometries are solved by Walas Phase Equilibiia in Chemical Engineering, Butterworths, 1985). 

A more general, and for the moment, less detailed description of the progress of chemical reactions, was developed in the transition state theory of kinetics. This approach considers tire reacting molecules at the point of collision to form a complex intermediate molecule before the final products are formed. This molecular species is assumed to be in thermodynamic equilibrium with the reactant species. An equilibrium constant can therefore be described for the activation process, and this, in turn, can be related to a Gibbs energy of activation ... 

Chemical equilibrium for a reaction is associated with the change in Gibbs free energy (AG ) ealculated as follows ... 

What Are the Key Ideas Tlic direction of natural change coi responds 10 the increasing disorder of energy and matter. Disorder is measured by the thermodynamic quantity called entropy. A related quantity—the Gibbs free energy—provides a link between thermodynamics and the description of chemical equilibrium. 

Why Do We Need to Know This Material The second law of thermodynamics is the key to understanding why one chemical reaction has a natural tendency to occur bur another one does not. We apply the second law by using the very important concepts of entropy and Gibbs free energy. The third law of thermodynamics is the basis of the numerical values of these two quantities. The second and third laws jointly provide a way to predict the effects of changes in temperature and pressure on physical and chemical processes. They also lay the thermodynamic foundations for discussing chemical equilibrium, which the following chapters explore in detail. 

What Do We Need to Know Already The concepts of chemical equilibrium are related to those of physical equilibrium (Sections 8.1-8.3). Because chemical equilibrium depends on the thermodynamics of chemical reactions, we need to know about the Gibbs free energy of reaction (Section 7.13) and standard enthalpies of formation (Section 6.18). Ghemical equilibrium calculations require a thorough knowledge of molar concentration (Section G), reaction stoichiometry (Section L), and the gas laws (Ghapter 4). 

The criterium for chemical equilibrium is that the Gibbs free energy is at its minimum ... 

The open cell discussed was considered as an equilibrium cell since equilibrium was established across each individual interface. However, the cell as a whole is not in equilibrium the overall Gibbs energy of the full reaction is not zero, and when the circuit is closed, an electric current flows that is attended by chemical changes (i.e., a spontaneous process sets in). 

In the knowledge that the Gibbs energy of a crystal containing a small number of intrinsic defects is lower than that of a perfect crystal, the defect population can be treated as a chemical equilibrium. In the case of vacancies we can write... 

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