Van der Waals critical point

ID: van-der-waals-critical-point

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 is
Dividing these relations gives , hence
Substitution 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]
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 , and
The 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.

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