The critical temperature of a substance is defined as the temperature above which its vapor cannot be liquefied, regardless of pressure. To determine it experimentally, one approach involves maintaining a constant volume while heating the liquid until no liquid remains, identifying the corresponding pressure as the critical pressure. Another method is to use a constant pressure calorimeter to track temperature changes and observe where the temperature levels out, indicating the transition point. Additionally, surface tension measurements can help estimate the critical temperature, as it approaches zero at this point. Understanding vapor-liquid equilibrium (VLE) and pressure-volume-temperature (PVT) behavior is crucial for accurate calculations and experiments.