Kinetic approach to condensation: Diatomic gases with dipolar molecules

We derive a kinetic equation for rarefied diatomic gases whose molecules have a permanent dipole moment. Estimating typical parameters of such gases, we show that quantum effects cannot be neglected when describing the rotation of molecules, which we thus approximate by quantum rotators. The intermolecular potential is assumed to involve an unspecified short-range repulsive component and a long-range dipole-dipole Coulomb interaction. In the kinetic equation derived, the former and the latter give rise, respectively, to the collision integral and a self-consistent electric field generated collectively by the dipoles (as in the Vlasov model of plasma). It turns out that the characteristic period of the molecules' rotation is much shorter than the time scale of the collective electric force and the latter is much shorter than the time scale of the collision integral, which allows us to average the kinetic equation over rotation. In the averaged model, collisions and interaction with the collective field affect only those rotational levels of the molecules that satisfy certain conditions of synchronism. It is then shown that the derived model does not describe condensation; i.e., permanent dipoles of molecules cannot exert the level of intermolecular attraction necessary for condensation. It is argued that an adequate model of condensation must include the temporary dipoles that molecules induce on each other during interaction, and that this model must be quantum, not classical.

Figure 1

A comparison of the equation of state (94) (dotted line) and that of the van der Waals gas, Eq. (95) (solid line), for ${\eta }_B=3.3375$ and ${\eta }_W=4.6171$. The black dot corresponds to the case of equality in criterion (89). The dashed line shows the state equation of the ideal gas, $p=1/V$.