Critical temperature

The critical temperature of a material is the temperature above which distinct liquid and gas phases do not exist. As the critical temperature is approached, the properties of the gas and liquid phases become the same. Above the critical temperature, there is only one phase. The critical pressure is the vapor pressure at the critical temperature. The critical molar volume is the volume of one mole of material at the critical temperature and pressure. On diagrams showing thermodynamic properties for a given substance, the point at critical temperature and critical pressure is called the critical point of the substance.

Critical properties vary from material to material, just as is the case for the melting point and boiling point. Critical properties for many pure substances are readily available in the literature. Obtaining critical properties for mixtures is somewhat more problematic.

For pure substances, there is an inflexion point in the critical isotherm on a PV diagram. This means that at the critical point:

[itex]\left(\frac{\partial P}{\partial V}\right)_T = \left(\frac{\partial^2P}{\partial V^2}\right)_T = 0[itex]

This relation can be used to evaluate two parameters for an equation of state in terms of the critical properties.

Sometimes a set of reduced properties are defined in terms of the critical properties, ie.:

[itex]T_r = T/T_c[itex]
[itex]P_r = P/P_c[itex]
[itex]V_r = V/V_c[itex]

The principle of corresponding states indicates that substances at equal reduced pressures and temperatures have equal reduced volumes. This relationship is approximately true for many substances, but becomes increasingly inaccurate for large values of Pr

Two immiscible liquids, such as oil and water, will also have a critical temperature and pressure at which the two phases will become consolute.

Critical temperature of selected elements

ElementCritical temperature (°C)
Argon-122.29
Arsenic1400
Bromine315
Chlorine143.8
Fluorine-128.85
Helium-267.96
Hydrogen-240.17
Iodine546
Krypton-63.7
Mercury1477
Neon-228.75
Nitrogen-146.9
Oxygen-118.57
Phosphorus721
Selenium1493
Sulfur1041
Xenon16.58

Critical temperature of selected molecules

ElementCritical temperature (°C)Critical pressure (atm)
Ammonia (NH3)132115
Carbon Dioxide (CO2)31.277
Carbon Monoxide (CO)-14135.9
Ethanol (C2H6O)21665
Methane (CH4)-8245.8
Propane (C3H8)9742
Sulfur Dioxide (SO2)15777.8
Water (H2O)374217.8

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