Chapter 8 : Chemical Reaction Equilibria

Section 2 : Standard Enthalpy and Gibbs free energy of reaction
 
8.2 Standard Enthalpy and Gibbs free energy of reaction

From the foregoing discussion it may be apparent that a chemical reaction may be carried out in diverse ways by changing temperature, pressure, and feed composition. Each of the different conditions would involve different conversions and heat effects. Thus there is need to define a “standard” way of carrying out a reaction. If all reactions were carried out in the same standard manner, it becomes possible to compare them with respect to heat effects, and equilibrium conversion under the same conditions. In general all reactions are subject to heat effects, whether small or large. A reaction may either release heat (exothermic) or absorb heat (endothermic). However, it is expected that the heat effect will vary with temperature. Thus, there is a need to develop general relations that allow computation of the heat effect associated with a reaction at any temperature.

Consider a reaction of the following form:

(8.1)

The reactants (A1 and A2) and products (A3 and A4) may be gaseous, liquid or solid. The term is the stoichiometric coefficient corresponding to the chemical species Ai. For the purpose of development of the reaction equilibria relations it is convenient to designate the stoichiometric numbers of the reactants as negative, while those of the products as positive. This is to signify that reactants are depleted in proportion to their stoichiometric numbers, while the products are formed in proportion to their stoichiometric numbers. Consider, for example, the following gas-phase reaction: