In my previous two posts (here and here), I described the ways by which J. Willard Gibbs’s work on thermodynamics spread through the European science community. In this post I describe another way Gibbs’s work spread and it began with early admirer of Gibbs, Johannes Diderik van der Waals (1837-1923), a Dutch theoretical physicist.  It was really this pathway that ended up validating Gibbs and putting him on the world stage. 

Rakhuis Roozeboom needed help

As recounted by Daub[1], the relevant timeline started in 1884 when Bakhuis Roozeboom (1854-1907), a Dutch chemist, began his experimental research on the complex phase equilibria of the hydrates of water with different elements and compounds, including HBr.  The complexity of such studies was enhanced by the fact that water could form multiple hydrates with any such given species.  Thus, such systems provided a tremendously rich and complex world for the study of multiple species and multiple phases—solid, liquid and vapor. 

For each of his systems, Roozeboom carefully mapped out the T-P-x_i data for the liquid and multiple solid phases involved and then used the data to create fascinating phase diagrams.  For the water plus HBr system, he arrived at diagrams that he couldn’t fully explain, which is when he turned to van der Waals for help. 

Gibbs through van der Waals to the rescue!

Van der Waals saw this problem as an opportunity to apply Gibbs’s work and so developed a set of thermodynamic equations based on the phase rule and also on the Clausius-Clapeyron equation and ultimately solved the puzzle, providing in so doing insight into the existence of a new hydrate (HBr*H₂O), a discovery that wouldn’t have been possible without the guiding theoretical work of Gibbs.  In his publications on this success, Roozeboom proposed that chemists adopt Gibbs’ phase rule as the structure for classifying complex dissociation equilibria.  Thus were the Dutch among the first to experimentally validate Gibbs and establish his theories in chemistry.

I need to read Roozeboom’s work to fully understand what was behind his “eureka!” moment upon reading Gibbs

While Gibbs spent little time writing about the application of this work to industry, others did the job for him, with Roozeboom being one of the early adopters.  For example, prior to Gibbs, there had been little to no theoretical understanding of metal alloys.   Roozeboom used Gibbs’ work to interpret the properties of steel as a two-component system and in so doing turned metallurgy into a modern science.  It wasn’t long before such successes inspired others in other fields.  Soon Gibbs’ work became the means by which to bring theoretical understanding to other industrial chemistries.  Wrote Tammann, “No abstract work has had such decisive influence on the development of basic industries as Gibbs’ memoir on heterogeneous equilibria.”[2]

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References

[1] Daub, E.E., 1976. “Gibbs Phase Rule: A Centenary Retrospect.” J. Chem. Educ. 53 (12) (December): 747–51.

[2] Crowther, J. G. 1937. Famous American Men of Science. W.W. Norton & Company, inc. Reference to G. Tammann’s writing, p. 279.

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