Mass variables and chemical potentials in the Gibbs and De Donder formulations of chemical equilibrium (Q862880)

The author considers chemical equilibria in closed systems. The energy variations are known to be equivalent when considering either De Donder's or Gibbs' formulations. The author first recalls these two formulations which link in a linear way the energy variations to that of masses. In the first case, the masses are the current masses of all the chemical substances which are involved and stoichiometric constraints must be imposed. In the second case, the masses of non-independent species are eliminated. The author recalls the Gibbs-Duhem relation between the remaining masses. The main goal of the paper is to prove the equivalence of these formulations introducing appropriate linear combinations of the masses and of the stoichiometric coefficients of the system. This leads to a modified Gibbs-Duhem relation. An example of such linear combinations is given in an appendix for an ion exchange reaction. The author also formulates a multi-phase chemical equilibrium problem in De Donder's formulation using Lagrange multipliers. He ends the paper claiming that De Donder's formulation allows to treat constraints such as electro-neutrality among ionic species in electrolyte solutions.