Nucleation rates of supersaturated vapors near the conditions for the critical line for each pair of 1,2- or 1,3-propanediol and carbon dioxide or sulfur hexafluoride at total system pressures of P=0.10, 0.20, and 0.30 MPa have been measured in a flow diffusion chamber. Critical parameters, i.e., temperatures and pressures, of the binary systems versus compositions were semiempirically evaluated. It was found experimentally that there is an area of parameters in the PTx phase diagram, for each pair of vapor and carrier gas investigated in the present research, for which critical embryo phase transitions of the first order take place (where P, T, and x are pressure, temperature, and embryo composition, respectively). The nucleation rate surface singularity and a gap in the number of molecules in critical embryos reflect this area. Shifts of the phase transition temperatures can be initiated by increasing the pressure (or concentration) of the carrier gas. This behavior is peculiar for binary systems. It is well-known that no liquid-liquid phase transitions can exist for a one-component system. At least a binary solution is required for liquid-liquid phase transitions. This means that vapor nucleation of the investigated substances in the carrier gas atmosphere can be considered as nucleation of a binary vapor-gas system. A schematic diagram for the possible metastable vapor conditions is presented. On the basis of our experimental results, one can assume that there exists a surface describing the parameters related with a phase transition of the first order in critical embryos. This surface is located within the volume of the possible vapor metastable conditions.