THERMODYNAMICS OF FLUIDS IN QUENCHED DISORDERED MATRICES

Using the replica method, we derive the thermodynamic relations for a fluid in equilibrium with a quenched porous matrix. In particular, the appropriate Gibbs-Duhem equation is obtained as well as the equivalence between grand canonical and canonical ensembles. The exact compressiblity and virial equations are derived. Whereas the compressibility equation remains a direct and practical way to obtain the adsorption isotherm, the virial equation involves terms which do not relate easily to the properties of the fluid/matrix system. This explains the inconsistency between previous theoretical predictions and computer simulation results.