It is proposed that interface reaction barriers in binary A/B diffusion couples lead to the absence of phases predicted by the equilibrium phase diagram, provided that the diffusion zones are sufficiently thin (“thin film case”). With increasing thickness of the diffusion zones the influence of interface reaction barriers decreases and the simultaneous existence of diffusion-controlled growth of all equilibrium phases is expected (“bulk case”). First-phase and different modes of second-phase formation in the diffusion zones as well as the influence of impurities are discussed with specific reference to silicide formation. For this discussion the concept of a critical thickness of the first forming phase is introduced, below which a second compound phase cannot grow simultaneously with the first one.