Van der Waals critical point 2026-10-14
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 . The short calculation isDividing these relations gives , henceSubstitution gives the Van der Waals law of corresponding states and the parameter-independent ratio . That ratio belongs to this equation of state; reducing a real fluid's variables does not enforce it.[ref]
Statistical Physics by David Tong. §5.1.3, equations 5.7–5.8: critical values, reduced equation and compressibility ratio
An exact rearrangement of the reduced critical Van der Waals isotherm makes its flatness visible:The first nonzero departure near is . On the critical particle volume approached from , 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.
Van der Waals isotherm 2026-10-14
A Van der Waals isotherm is the pressure–particle volume curve at a fixed temperature. Put , , and , using the Van der Waals critical point values below. Then the existing Van der Waals law of corresponding states becomesAll curves in the figure are calculations in this reduced model.
Van der Waals isotherms below, at and above the Van der Waals critical point
. The dashed subcritical homogeneous continuation contains an unstable red segment. The green Maxwell construction plateau describes equilibrium phase coexistence; the two shaded areas are equal. Curves are model calculations, not carbon dioxide measurements. Details.For a uniform thermodynamic phase, the isothermal compressibility isThus the upward-sloping portion of a subcritical Van der Waals isotherm has : compression would reduce pressure, allowing a density disturbance to grow. It is mechanically unstable. The spinodal points bound that portion; setting the derivative to zero gives their curve . Negative slope alone guarantees only local mechanical stability: portions between the spinodal and the phase coexistence endpoints have metastability. Equilibrium replaces the entire interval between those endpoints, including these metastable portions, by a Maxwell construction plateau.[ref]
Statistical Physics by David Tong. §5.1, equation 5.3 and §5.1.1, Maxwell Construction and Meta-Stable States: unstable middle branch and coexistence versus spinodal
