## Abstract

The thermodynamic and structural properties of H_{2}O-CO_{2} mixtures along two supercritical isotherms at 773.15 and 1073.15 K in the pressure range from 0.2 to 30 kbar have been investigated by the NVT and NPT Monte Carlo method using the TIP4P and MSM3 effective intermolecular potentials for H_{2}O and CO_{2}, respectively. Calculated excess volumes of mixing are in very good agreement with experimental data at low pressure. Results suggest that non-ideal mixing still occurs at 1073.15 K and at pressures up to 7 kbar. Although structural analysis shows that there is some clustering of H_{2}O molecules in the mixtures relative to the pure fluids, this does not appear to correlate with excess volumes. The most pronounced clustering occurs at high pressure and low temperature while the largest excess volumes occur at low pressure and low temperature. An equation is given to calculate excess volumes of mixing at different pressures and compositions along both isotherms. It has the following mathematical expression: V_{ex} = [a_{1}X_{CO2}(1 - X_{CO2}) + b_{1} X_{CO2} 1n(X_{CO2})] (a + bP + c√P + d/P + e/P^{2} + fP^{2}) and reproduces calculated V_{ex} with a standard deviation of 0.8 and 0.4 cm^{3}/mol at 773.15 and 1073.15 K, respectively.

Original language | English |
---|---|

Pages (from-to) | 53-65 |

Number of pages | 13 |

Journal | Chemical Geology |

Volume | 133 |

Issue number | 1-4 |

Publication status | Published - 22 Nov 1996 |

## Keywords

- Excess properties
- HO-CO mixture
- Statistical thermodynamics

## Fingerprint

Dive into the research topics of 'Monte Carlo simulation of H_{2}O-CO

_{2}mixtures to 1073.15 K and 30 kbar'. Together they form a unique fingerprint.