Phase equilibrium data were measured for the binary systems of n-pentane + cyclohexane at (293.20, 298.17, and 303.17) K and 1-hexene + 2-propanol at (293.18, 303.17, and 313.16) K. The experimental measurements were conducted using a static-synthetic total pressure apparatus. The overall compositional data (T-P-z) were converted to the coexisting phases at equilibrium (T-P-x-y) using material balances and thermodynamic models. The thermodynamic models followed the combined method featuring either the Wilson or non-random two-liquid activity coefficient models and the ideal gas law. The models provided an excellent fit to the experimental data. The binary system of 1-hexene + 2-propanol exhibited positive deviation from Raoult's law, resulting in the formation of a homogeneous azeotrope for all the measured isotherms.