The constitutive relationships required for the parameterization of multiphase flow and transport problems are of critical importance to hydrologic modeling. Recently, a hypothesis has been developed that predicts a functional relationship between capillary pressure, saturation, and interfacial area. A network model was developed to test this hypothesis. Microscale physical processes were simulated and volume averaging was used to derive the macroscopic measures of saturation and fluid-fluid interfacial area per volume of porous media. Results indicate that a smooth, though complex, functional relationship exists at the continuum scale. These results have direct relevance to constitutive theory and the modeling of nonaqueous phase liquid dissolution processes. ¿ American Geophysical Union 1996