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The oxygen isotope partition function ratio of water and the structure of liquid water

Journal of Physical Chemistry

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DOI: 10.1021/j100725a062

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Abstract

By means of the CO2-equilibration technique, the temperature dependence and absolute values of the oxygen isotope partition function ratio of liquid water have been determined, often at 1?? intervals, from -2 to 85??. A linear relationship between In (Q2/Q1) (H2O) and T-1 was obtained that is explicable in terms of the Bigeleisen-Mayer theory of isotopic fractionation. The data are incompatible with conventional, multicomponent mixture models of water because liquid water behaves isotopically as a singly structured homogeneous substance over the entire temperature range studied. A two-species model of water is proposed in which approximately 30% of the hydrogen bonds in ice are broken on melting at 0?? and in which this per cent of monomer changes by only a small amount over the entire liquid range. Because of the high precision and the fundamental property determined, the isotopic fractionation technique is particularly well suited to the detection of thermal anomalies. No anomalies were observed and those previously reported are ascribed to under-estimates of experimental error.

Additional Publication Details

Publication type:
Article
Publication Subtype:
Journal Article
Title:
The oxygen isotope partition function ratio of water and the structure of liquid water
Series title:
Journal of Physical Chemistry
DOI:
10.1021/j100725a062
Volume
73
Issue:
5
Year Published:
1969
Language:
English
Larger Work Type:
Article
Larger Work Subtype:
Journal Article
Larger Work Title:
Journal of Physical Chemistry
First page:
1553
Last page:
1558
Number of Pages:
6