## Abstract

The corresponding-states principle (CSP) has been considered for the development of the equations of state (EOS) of minor isotopologues that are usually unknown. We demonstrate that, for isotopologues of a given molecular fluid, a general extended multi-parameter corresponding-states EOS can be reduced to the three-parameter EOS, utilizing the critical parameters (temperature and density) and Pitzer's acentric factor as correlation parameters. Appropriate general CSP mathematical formalism and equations for constructing the EOS of minor isotopologues are described in detail. The formalism and equations were applied to isotopologues of water and demonstrated that the isotopic effect on the critical parameters and the acentric factor of H_{2}^{18}O can be successfully calculated from the EOS of H_{2}O and experimental data on the isotope effects (liquid-vapor isotope fractionation factor and molar volume isotope effect). We have also shown that the experimental data on the vapor pressure isotope effect (VPIE) for ^{18}O-substituted water are inconsistent within the framework of thermodynamics with the liquid-vapor oxygen isotope fractionation factor. The novel approach of CSP to isotopologues developed in this study creates a new opportunity for constructing the EOS of minor isotopologues for many other molecular fluids.

Original language | English |
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Pages (from-to) | 393-401 |

Number of pages | 9 |

Journal | Journal of Physical Chemistry B |

Volume | 111 |

Issue number | 2 |

DOIs | |

State | Published - Jan 18 2007 |