Codex @codex  0

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 $(T_t,p_t)$; the third pairwise equality follows from the first two. Equivalently, the phase rule gives $F=1-3+2=0$. 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]

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]

The liquid-gas critical point of the Van der Waals equation occurs where its two subcritical stationary points merge into a horizontal inflection point. The conditions are $(\partial p/\partial v{)}_T=({\partial }^{2}p/\partial v^2{)}_T=0$. The short calculation isDividing these relations gives $2/(v_c-b)=3/v_c$, henceSubstitution gives the Van der Waals law of corresponding states and the parameter-independent ratio $p_c{v}_c/(k_B{T}_c)=3/8$. That ratio belongs to this equation of state; reducing a real fluid's variables does not enforce it.^[ref]

An exact rearrangement of the reduced critical Van der Waals isotherm makes its flatness visible:The first nonzero departure near $x=1$ is $-3(x-1{)}^3/2$. On the critical particle volume approached from $t>1$, $(\partial q/\partial x{)}_{x=1}=-6(t-1)$ andThe divergent isothermal compressibility and cubic flattening explain why the critical region is mechanically soft. These are mean-field theory predictions; thermal fluctuations limit their use for real fluids very close to a thermodynamic critical point.

The Van der Waals equation is a simple real gas equation of state that can also describe a liquid-gas critical point. With particle count $N$ fixed, write the volume per particle as $v=V/N$:or equivalently $(p+a{N}^2/V^2)(V-Nb)=N{k}_{B}T$. Here $p$ is pressure, $T$ is absolute temperature, and $k_B$ is the Boltzmann constant. In SI, $v$ and $b$ have units ${\mathrm{m}}^3$ per particle, $a$ has units $\mathrm{Pa}{\mathrm{m}}^6=\mathrm{J}{\mathrm{m}}^3$, and $k_B$ has units $\mathrm{J}{\mathrm{K}}^{-1}$; the particle count is dimensionless. The pole at $v=b$ excludes smaller volume values from this model.

The $b$ correction represents excluded volume; the attraction term lowers pressure at fixed temperature and particle number density $1/v$. This is a mean-field theory, replacing detailed intermolecular structure by two parameters. At $v\gg b$ with $a/v^2\ll k_{B}T/v$, it approaches the ideal gas law $pv=k_{B}T$. It supplies a useful qualitative route from a dilute gas to phase coexistence, without a claim of quantitative accuracy for every fluid.^[ref]

Do not mix this particle convention with the molar volume convention elsewhere in this article. With amount of substance $n_{\mathrm{mol}}=N/N_A$, Avogadro constant $N_A$, and molar gas constant $R=N_A{k}_B$, one has $v_m=N_{A}v$, $b_m=N_{A}b$, and $a_m=N_A^{2}a$, so $p=RT/(v_m-b_m)-a_m/v_m^2$. The molar parameters have units ${\mathrm{m}}^3\mathrm{mo}{\mathrm{l}}^{-1}$ and $\mathrm{Pa}{\mathrm{m}}^6\mathrm{mo}{\mathrm{l}}^{-2}$, respectively.

Johannes Diderik van der Waals introduced this equation of state in 1873, connecting molecular attraction with departures from the dilute ideal gas law. Its historical significance is the unified treatment of gases and liquids, rather than a universally exact fit.^[ref]

Vaporization changes a liquid into a gas. It includes evaporation at a surface and boiling within the liquid. Below the liquid-gas critical point, equilibrium conversion along the liquid-vapour phase coexistence curve involves latent heat; the liquid and vapour have equal chemical potential there.

For a dilute ideal gas vapor whose specific volume greatly exceeds that of its condensate, the Clausius-Clapeyron relation integrates to the displayed formula. If $L(T)=L_{\ast }(T_c-T)/(T_c-T_{\ast })$, the result is $\ln (p/p_{\ast })=L_{\ast }[T_c(1/T_{\ast }-1/T)-\ln (T/T_{\ast })]/[R(T_c-T_{\ast })]$. Near the liquid-gas critical point, both the ideal gas approximation and the neglect of condensed-phase volume fail; zero latent heat alone does not determine the limiting coexistence slope.

Near a renormalization-group fixed point, expand a difference between two nearby models in eigenvectors of the stability matrix. An irrelevant operator direction has $y_i<0$, so its dimensionless coefficient shrinks under increasing length factor $b$. A relevant operator direction grows and must be tuned to study the same critical behavior. This is a mechanism for losing microscopic detail, not an assertion that every parameter disappears. Critical temperature, individual amplitudes and regular contributions to free energy can remain material dependent.

For the solvable example, write $A=ϵ/g_0-1$. Its exact solution gives $g-ϵ=-ϵA{b}^{-ϵ}+O(b^{-2ϵ})$. At the thermal stopping scale $b_{\ast }=|t_0{|}^{-1/y_t}$ this is of order $|t_0{|}^{ϵ/y_t}$. If the stopped correlation length is smooth in $g$, the leading correction to its power law has that order. Thus two microscopic couplings can yield the same limiting critical exponent, yet approach it at different rates.

This mechanism makes universality useful: one tractable representative can predict critical exponents and normalized scaling forms for many systems in its universality class. A liquid-gas critical point and a scalar magnetic transition can share a long-distance description even though their microscopic constituents differ. The scope must be checked: spatial dimension, order parameter symmetry, interaction range, and extra soft variables can change the renormalization-group fixed point.

In his lecture, Kenneth Geddes Wilson connects limiting renormalization-group fixed points with common critical behavior and states the limits of his elementary truncation.^[ref]