A triple point is a temperature–pressure pair at which three distinct bulk thermodynamic phases of a one-component substance coexist in thermodynamic equilibrium. In the familiar solid–liquid–gas case, their three phase coexistence curves meet. Other combinations, such as two crystal polymorphs and a liquid, also qualify: “triple” counts thermodynamic phases, rather than states-of-matter categories.
For the same substance, the chemical potential in each thermodynamic phase must agree:There are two independent equality conditions for two controls, temperature and pressure. Generically they select an isolated pair ; the third pairwise equality follows from the first two. Equivalently, the phase rule gives . This counts independent intensive controls, not phase fractions: changing the amounts of the three thermodynamic phases need not change the ideal bulk temperature and pressure, provided all three remain present. Different sets of crystal polymorphs can give different triple points for the same substance.[ref]
Gibbs Phase Rule (MIT 10.213 course material). Gibbs Phase Rule, three-phase count and pressure–temperature diagram discussion
At a liquid-gas critical point, the two fluid thermodynamic phases instead merge, and their mass density difference and latent heat vanish. It is the endpoint of the liquid–gas phase coexistence curve, rather than a meeting of three distinct thermodynamic phases. The regular independent-equality count used for a triple point cannot explain this merger. A triple point can retain finite mass density and entropy differences between all three thermodynamic phases.[ref]
Statistical Physics by David Tong. §5.1.2, printed p. 141: vanishing liquid–gas discontinuity at the critical point; Figure 41 separates it from the three-phase junction
The triple point of a substance is the specific temperature and pressure at which the three phases of that substance—solid, liquid, and gas—can coexist in thermodynamic equilibrium. At this unique point, the solid, liquid, and vapor phases of the substance are in balance, meaning that any change in one phase can lead to the formation or conversion into another phase without altering the overall pressure and temperature.
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