Statistical Mechanics – How Can the Pressure Be Zero for a Gas Obeying the van der Waals Equation?

physical-chemistrypressurestatistical mechanicstemperature

According to Halliday-Resnick, if the intermolecular forces are large enough, then the measured pressure $p$ of a gas that obeys the van der Waals equation of state, $\left(p+\frac{an^2}{V^2}\right)(V-nb) = nRT$, can be $0$.

The explanation given is that the intermolecular forces which cause the pressure correction factor $\frac{an^2}{V^2}$ may be enough to prevent particles from bouncing off a wall of the container at all, thus no pressure.

However, if the pressure correction is becoming stronger, why isn't it instead $p+\frac{an^2}{V^2}$ that becomes $0$ as $\frac{an^2}{V^2}$ grows more negative? Do I simply have a conceptual misunderstanding of the van der Waals equation?

Additionally, using the book’s explanation (assuming $p=0$), I solved for molar volume and obtained a quadratic with two solutions. What is the physical interpretation of these two molar volumes (ie why isn’t there just 1?)

Best Answer

If I understand your question, then the following might help. Solve the van der Waals equation for p and you get: $$p=\frac{nRT}{V-nb}-a\frac{n^2}{V^2}$$ So note that the pressure is reduced from what it would be if the factor $a$ was 0.