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 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.
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