Anomalous properties of supercooled water. Heat capacity, expansivity, and proton magnetic resonance chemical shift from 0 to -38°

C. A. Angell, J. Shuppert, J. C. Tucker

Research output: Contribution to journalArticle

247 Scopus citations

Abstract

Expectations of a rapidly increasing heat capacity for water at low temperatures are confirmed by differential scanning calorimetry. Cp is found to rise very rapidly from 18 to 29 cal mol-1 deg-1 between -10° and the homogeneous nucleation temperature, -40°. Proton magnetic resonance chemical shift measurements suggest this behavior is associated with a cooperative acceleration in hydrogen bond strength or formation rate at low temperatures. It is shown that in light of these results the existence of vitreous waters which soften and crystallize near 150 K is paradoxical. To resolve the paradox the existence below the homogeneous nucleation temperature of a λ-type transition similar to that encountered in liquid sulfur is postulated. Its origin is tentatively accounted for in terms of the cooperative bond lattice model. It is apparent that the positive volume change associated with hydrogen bond formation plays a dominant role in determining the observed constant pressure behavior on cooling, the positive volume change itself being a consequence of the geometry of formation of the four coordinate random network.

Original languageEnglish (US)
Pages (from-to)3092-3099
Number of pages8
JournalJournal of physical chemistry
Volume77
Issue number26
DOIs
StatePublished - Jan 1 1973
Externally publishedYes

ASJC Scopus subject areas

  • Engineering(all)
  • Physical and Theoretical Chemistry

Fingerprint Dive into the research topics of 'Anomalous properties of supercooled water. Heat capacity, expansivity, and proton magnetic resonance chemical shift from 0 to -38°'. Together they form a unique fingerprint.

  • Cite this