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Transport of water in small pores.

Experimental measurements of the thermal expansion coefficient (alpha), permeability (k), and diffusivity (D) of water and 1 M solutions of NaCl and CaCl(2) are interpreted with the aid of molecular dynamics (MD) simulations of water in a 3 nm gap between glass plates. MD shows that there is a layer approximately 6 A thick near the glass surface that has alpha approximately 2.3 times higher and D about an order of magnitude lower than bulk water. The measured D is approximately 5 times lower than that for bulk water. However, when the MD results are averaged over the thickness of the 3 nm gap, D is only reduced by approximately 30% relative to the bulk, so the measured reduction is attributed primarily to tortuosity of the pore space, not to the reduced mobility near the pore wall. The measured alpha can be quantitatively explained by a volume-weighted average of the properties of the high-expansion layer and the "normal" water in the middle of the pore. The permeability of the porous glass can be quantitatively predicted by the Carman-Kozeny equation, if 6 A of water near the pore wall is assumed to be immobile, which is consistent with the MD results. The properties and thickness of the surface-affected layer are not affected significantly by the presence of the dissolved salts.