Capillary pressure relationships in a porous medium determine the distribution of immiscible fluids under static conditions and can largely influence the movement of the fluids when the system is not at equilibrium. The capillary pressure-saturation curves measured here for hydrocarbon oil-water do not have a constant capillary pressure ratio with saturation when compared to the water-air system, and changes in ratio were found when comparing the water-air curves measured at different temperatures. Thus, the scaling theory based on interfacial tensions and contact angles does not adequately account for differences in capillary pressures due to different fluid pairs or temperatures. When the capillary pressure-saturation relationship is extended to the calculation of relative permeabilities and the prediction of fluid flow in the subsurface, the differences in measured and scaled capillary pressure curves lead to differences in the predicted flow rates and saturations of the immiscible fluids in the subsurface. Thus, care must be used when applying capillary pressure-saturation data from one fluid system to that of another, or when applying it to different conditions.