Abstract. -Phase equilibria between regions of different thickness in thin liquid films stabilized by colloidal particles are investigated using a quasi-two-dimensional thermodynamic formalism. Appropriate equilibrium conditions for the film tension, normal pressure, and chemical potential of the particles in the film are formulated, and it is shown that the relaxation of these parameters occurs consecutively on three distinct time scales. Film stratification is described quantitatively for a hard-sphere suspension using a Monte-Carlo method to evaluate thermodynamic equations of state. Coexisting phases are determined for systems in constrained-and full-equilibrium states that correspond to different stages of film relaxation.Drainage of thin liquid films often involves spontaneous formation of coexisting regions of different, but uniform, thickness. For example, circular black-film spots can be seen in soap bubbles prior to breakup. Such a stratification phenomenon is particularly interesting in films stabilized by colloidal particles, micelles, or polyelectrolytes, where the thinning occurs through a series of stepwise transitions between film states characterized by the thickness commensurate with the size of the stabilizing particles. In experiments with horizontal films [1, 2], such transitions occur by rapid formation of circular regions of a smaller thickness, followed by a much slower expansion. In investigations of vertical films, up to seven coexisting parallel stripes of different thickness have been observed [3].Film stratification has recently been intensively studied [1][2][3][4][5][6][7][8] because of the relevance of the problem for understanding structural colloidal forces. In particle-stabilized thin liquid films, the structural forces depend on the film thickness in an oscillatory manner due to particle layering [9]. Equilibrium values of the film thickness result from the balance between the normal pressure in the film (which includes the oscillatory structural force) and the outside pressure [6,7,10]. We find, however, that the normal-stress balance used alone in descriptions of the film stratification phenomenon is insufficient-the mechanical equilibrium between regions (phases) of different thickness requires also the lateral force balance. Since the lateral balance has not been included in the available theories, understanding of an essential aspect of c EDP Sciences