The law of the geometric mean for the vapour pressure isotope effect in the series HOH, HOD, and DOD is not obeyed; rather In [P(H2O)/P(D2O)]/ln [P(H2O)/P(HOD)]= 1·91 ± 0·03, so the equilibrium constant for the reaction HOH + DOD = 2 HOD, K1(condensed), is significantly larger than K1(dilute gas); the difference varies from 1·5 ± 0·5% at –25 °C to 0·3 ± 0·1% at 75 °C.
W. A. Van Hook, J. Chem. Soc., Chem. Commun., 1972, 479 DOI: 10.1039/C39720000479
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