Translation of a paper of J D van der Waals

October 14, 2007

The translation of a Dutch paper (PhD thesis?) of van der Waals into English by J S Rowlinson is available here (Unfortunately, I have no access to the soft copy version):

Van der Waals justifies the choice of minimization of the (Helmholtz) free energy as the criterion of equilibrium in a liquid-gas system (Sections 1–4). If densityrgr is a function of height h then the local free energy density differs from that of a homogeneous fluid by a term proportional to (d 2 rgr/dh 2); the extra term arises from the energy not from the entropy (Section 5). He uses this result to show howrgr varies with h (Section 6), how this variation leads to a stable minimum free energy (Section 7), and to calculate the capillary energy or surface tensionsgr (Section 9). Near the critical pointsgr varies as (tau k tau)3/2, wheretau k is the critical temperature (Section 11). The paper closes with short discussions of the thickness of the surface layer (Section 12), of the difficulty of assuming thatrgr varies discontinuously with height (Section 14), and of the possible effect of derivatives of higher order than (d 2 rgr/dh 2) on the free energy and surface tension (Section 15).

Generally, the origin of the concept (and name) of spinodal decomposition is credited to van der Waals. I do not know if this document discusses that aspect of van der Waals’ work — I have to go to the library tomorrow.

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One Response to “Translation of a paper of J D van der Waals”


  1. […] of Metals lecture in 1968 [6] traces the name and the concept of spinodal to van der Waals, a link to whose paper is available here. It is also well known that the work of Cahn and Hilliard is but a continuum version of that of […]


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