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    Fisher 1981

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    t8e7w2ko

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    © All Rights Reserved
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    Nature Vol. 290 16 April 1981 The Kelvin equation and the capillary condensation of water L. R. Fisher, R. A. Gamble & J. Middiehurst CSIRO Division of Food Resesrch, PO Box 52, North Ryde, New South Wales 2113, Australia ‘The Kelvin equation’ relates the equilibrium vapour pressure of 4 Tiguid 10 the curvature of the lguid-rapour interface. It predicts that undersaturated vapours will condense in channels ‘of suficiently small dimensions. While the applicability of the Kelvin equation to organic liquids with meniscus radi as low as 44nm has been verified by direct experiment’ its applicability to ‘water for meniscus radi below 4 nm is unverified, and has been fused silica surfaces. Measurements were made at relative vapour pressures (P/P.) trom 0.996 down to 0.945, cor- responding o theoretical meniscus radi from ~120 to 9nm. We find only « small discrepancy between our experimental results and the Kelvin equation in the vapour pressure range covered, Provided that correct account is taken of the effect of the sdsorbed film, up t0 200 nm thick, on the meniscus shape, ‘The Kelvin equation forms the basis of critical nucleation theory’, and is widely used in the interpretation of such diverse phenomena as adhesion’, the enhanced solubility of small particles’ and the retention and transport of liquids in porous materials*"”, Because water is an important liquid in the above applications, we need direct experimental evidence concerning its capillary condensation behaviour. ‘Cross and Picknett"' have shown experimentally that water ‘obeys the Kelvin equation for meniscus radii > ~4um, but most applications of the equation involve much smaller radii. Other experiments have purported to show that the Kelvin equation grossly underestimates the degree of capillary condensation of, Water, but these results are now generally ascribed to the Presence of impurities", and there have been no reliable Studies in the important region covering menisci with rad

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