Thermodynamics of chemical reactions

This chapter is devoted to chemical equilibrium. We will use thermodynamics to answer two main questions: (1) ‘‘In which direction will a chemical reaction proceed?’’ and (2) ‘‘What is the composition of the system at equilibrium?’’ These are the oldest and most important questions in all of chemical thermodynamics for obvious reasons. The answers to these questions represent the foundation upon which all modern chemical technologies rest. Consider the following chemical reaction: . . . aA = bB ⇆ cC + dD. (5.1) . . . A, B, C, and D represent the chemical species participating in the reaction and a, b, c, and d are the stoichiometric coefficients of these species. We refer to the species on the left side of this chemical equation as reactants and those on the right as products. The reaction in Eq. (5.1) can either go forward, from left to right (reactants to products), or backward, from right to left (products to reactants). Therefore, we see that the definition of which we call reactants and which products is arbitrary. Assume that Eq. (5.1) occurs at constant temperature and pressure. Under these conditions, the direction of the reaction is determined by the sign of the change of the Gibbs free energy.