A deterministic technique for reliable phase stability analysis is described for the case in which asymmetric modeling (different models for vapor and liquid phases) is used. In comparison to the symmetric modeling case, the use of multiple thermodynamic models in the asymmetric case adds an additional layer of complexity to the phase stability problem. To deal with this additional complexity we formulate the phase stability problem in terms of a new type of tangent plane distance function, which uses a binary variable to account for the presence of different liquid and vapor phase models. To then solve the problem deterministically, we use an approach based on interval analysis, which provides a mathematical and computational guarantee that the phase stability problem is correctly solved, and that thus the global minimum in the total Gibbs energy is found in the phase equilibrium problem. The new methodology is tested using several examples, involving as many as eight components, with NRTL as the liquid phase model and a cubic equation of state as the vapor phase model. In two cases, published phase equilibrium computations were found to be incorrect (not stable). (c) 2005 Elsevier B.V. All rights reserved.