of its molecules, or say aθ, where a is a constant and θ is the absolute temperature. Hence, we may write the equation
aθ = (1/2)m̄v̄^2̄ = (3/2)PV̄ + (1/2)[sum]R̄r̄
where the heavy lines above the different expressions signify that the average values for single molecules are to be taken. In 1872, a student in the University of Leyden, Van der Waals, propounded in his thesis for the doctorate a specialization of the equation of the virial which has since attracted great attention. Namely, he writes it
aθ = (P + c/V^2)(V - b.)
The quantity b is the volume of a molecule, which he supposes to be an impenetrable body, and all the virtue of the equation lies in this term which makes the equation a cubic in V, which is required to account for the shape of certain isothermal curves.[1] But if the idea of an impenetrable atom is illogical, that of an impenetrable molecule is almost absurd. For the kinetical theory of matter teaches us that a molecule is like a solar system or star-cluster in miniature. Unless we suppose that in all heating of gases and vapors internal work is performed upon the molecules, implying that their atoms are at considerable distances, the whole kinetical theory of gases falls to the ground. As for the term added to P, there is no more than a partial and roughly approximative justification for it. Namely, let us imagine
- ↑ But, in fact, an inspection of these curves is sufficient to show that they are of a higher degree than the third. For they have the line V = o, or some line V a constant for an asymptote, while for small values of P, the values of d^2p/(dV)^2 are positive.
