Waals - Scientific Work

Scientific Work

The main interest of van der Waals was in the field of thermodynamics. He was much influenced by Rudolf Clausius' 1857 treatise entitled Über die Art der Bewegung, welche wir Wärme nennen (On the Kind of Motion which we Call Heat). Van der Waals was later greatly influenced by the writings of James Clerk Maxwell, Ludwig Boltzmann, and Willard Gibbs. Clausius' work led him to look for an explanation of Thomas Andrews' experiments that had revealed, in 1869, the existence of critical temperatures in fluids. He managed to give a semi-quantitative description of the phenomena of condensation and critical temperatures in his 1873 thesis, entitled Over de Continuïteit van den Gas- en Vloeistoftoestand (On the continuity of the gas and liquid state). This dissertation represented a hallmark in physics and was immediately recognized as such, e.g. by James Clerk Maxwell who reviewed it in Nature in a laudatory manner.

In this thesis he derived the equation of state bearing his name. This work gave a model in which the liquid and the gas phase of a substance merge into each other in a continuous manner. It shows that the two phases are of the same nature. In deriving his equation of state van der Waals assumed not only the existence of molecules (the existence of atoms was disputed at the time), but also that they are of finite size and attract each other. Since he was one of the first to postulate an intermolecular force, however rudimentary, such a force is now sometimes called a van der Waals force.

A second great discovery was published in 1880, when he formulated the Law of Corresponding States. This showed that the van der Waals equation of state can be expressed as a simple function of the critical pressure, critical volume, and critical temperature. This general form is applicable to all substances (see van der Waals equation.) The compound-specific constants a and b in the original equation are replaced by universal (compound-independent) quantities. It was this law which served as a guide during experiments which ultimately led to the liquefaction of hydrogen by James Dewar in 1898 and of helium by Heike Kamerlingh Onnes in 1908.

In 1890, van der Waals published a treatise on the Theory of Binary Solutions in the Archives Néerlandaises. By relating his equation of state with the Second Law of Thermodynamics, in the form first proposed by Willard Gibbs, he was able to arrive at a graphical representation of his mathematical formulations in the form of a surface which he called Ψ (Psi) surface following Gibbs, who used the Greek letter Ψ for the free energy of a system with different phases in equilibrium.

Mention should also be made of van der Waals' theory of capillarity which in its basic form first appeared in 1893. In contrast to the mechanical perspective on the subject provided earlier by Pierre-Simon Laplace, van der Waals took a thermodynamic approach. This was controversial at the time, since the existence of molecules and their permanent, rapid motion were not universally accepted before Jean Baptiste Perrin's experimental verification of Albert Einstein's theoretical explanation of Brownian motion.