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Cited by 458

The DOI matches its Crossref record; 21 of the 21 references it cites were found in a registry or an index.

Melting and freezing of water in ordered mesoporous silica materials

Schreiber, Andreas, Ketelsen, Ingke, Findenegg, Gerhard H.·2001·Physical Chemistry Chemical Physics
DOI 10.1039/b010086m
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Abstract

The melting and freezing of water in a series of mesoporous silica materials with a hexagonal arrangement of unidimensional cylindrical pores and narrow pore-size distribution (MCM-41 with pore diameters from 2.9 to 3.7 nm, and SBA-15 with pore diameters from 4.4 to 11.7 nm) was studied by differential scanning calorimetry (DSC). A lowering of the melting temperature ΔTm = Tmb − Tm(R) up to 50 K was found for water in pores of decreasing radius R. The melting point data can be represented by a modified Gibbs–Thomson equation, ΔTm(R) = K/(R-t), with K = 52 K nm and t = 0.4 nm, in agreement with an earlier study of water in MCM-41 materials of pore width 2 to 4 nm. The value of K agrees with an estimate of the Gibbs–Thomson constant based on thermodynamic data for the normal melting point of ice, and the parameter t can be taken as the thickness of a surface layer of non-frozen water at the pore wall. DSC scans of the freezing of H2O and D2O in partially filled pores of SBA-15 reveal a peak pattern depending on the degree of pore filling ϕ. The different peaks are attributed to different states of the liquid in the pore space, iz. pore water in completely filled regions, and water as an adsorbed film at the pore wall. These two states coexist in a pore filling range ϕmin<ϕ<1, but only the film state exists at ϕ<ϕmin. The freezing peak of pore water appears to be nucleated by external bulk ice (at ϕ>1) but exhibits substantial supercooling at ϕ<1. On the other hand, the peak attributed to the freezing of film water exhibits no significant supercooling and is found at temperatures near 237 K, almost independent of ϕ and the pore width of the SBA-15 sample. The nature of a further (small) peak near 233 K is not yet understood. Contrary to cooling scans, only one DSC peak is observed in heating scans, independent of the pore filling. This finding indicates that the adsorbed liquid film is metastable relative to the frozen pore liquid.

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Metadata

Authors
Schreiber, A., Ketelsen, I., & Findenegg, G. H.
Venue
Physical Chemistry Chemical Physics
Publisher
Royal Society of Chemistry (RSC)
Published
2001
Volume
3
Issue
7
Pages
1185-1195
ISSN
  • 1463-9076 (ISSN-L)
  • 1463-9084
DOI
10.1039/b010086m
OpenAlex
W1984123249
Cited by
458
References
21
FWCI
6.74
Type
journal article
Language
en
Open access
closed

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