Abstract
THE thermodynamic properties of liquids trapped in microscopic pores or existing as very small, highly curved droplets are described by the Kelvin equation1. This equation forms the basis of critical nucleation theory2 and has been used in interpreting such diverse phenomena as adhesion3, the enhanced solubility of small particles2 and the retention and flow of liquids in porous materials4–6. The validity of the application of the Kelvin equation to such highly curved interfaces (where the mean radius of curvature can be in the range 1–100 nm) has been questioned1,4, but has never been tested by direct experiment. We have used multiple beam interferometry to observe the formation of capillary condensed liquid between crossed cylinders of molecularly smooth mica. We report here that the Kelvin equation is obeyed by cyclohexane menisci with mean radius of curvature as low as 4 nm. We further conclude that the application of the laws of thermodynamics, and the concept of a bulk surface tension, are valid in principle for such highly curved interfaces.
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FISHER, L., ISRAELACHVILI, J. Direct experimental verification of the Kelvin equation for capillary condensation. Nature 277, 548–549 (1979). https://doi.org/10.1038/277548a0
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DOI: https://doi.org/10.1038/277548a0
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