Calculation of the thermodynamic and transport properties of aqueous species at high pressures and temperatures: Standard partial molal properties of inorganic neutral species

Everett Shock, Harold C. Helgeson, Dimitri A. Sverjensky

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Abstract

Consideration of interactions between neutral aqueous species and H2O dipoles in terms of effective Born coefficients permits extension of the revised HKF (Helgeson, Kirkham and Flowers, 1981) equations of state (Tanger and Helgeson, 1988) for the standard partial molal properties of ionic species at high pressures and temperatures to include inorganic gases, acids, and other neutral aqueous species. Correlation algorithms similar to those used to estimate equation of state parameters for ions and electrolytes (shock, and Helgeson, 1988) have also been developed for neutral aqueous species. Calculation of the standard partial molal thermodynamic properties of dissolved inorganic gases as well as other neutral aqueous species as a function of pressure and temperature indicates that the standard partial molal volume (V̄0), heat capacity (C̄0 p), and entropy (S̄0), together with the apparent standard partial molal enthalpy of formation (ΔH̄0) of many of these species in the liquid phase minimize with increasing temperature at PSAT * * PSAT represents pressures corresponding to liquid-vapor equilibrium for the system H2O, except at temperatures <100°C where it refers to the reference pressure of 1 bar. and approach ∞ at the critical point of H2O. In the case of other neutral aqueous species such as SiO2(aq), V ̄0, C ̄0 p, S ̄0, and Δ H ̄0 behave as functions of temperature and pressure like those of electrolytes in the liquid phase and maximize with increasing temperature at PSAT, approaching - ∞ at the critical point of H2O. Which of these types of behavior is exhibited by V ̄0, C ̄) p, S ̄0, and Δ H ̄0 for a given neutral aqueous species depends in part on the relative volatility of the aqueous species and the effect of the species on solvent dipole-dipole interaction. Close agreement between predicted and experimentally determined equilibrium constants for gas solubility and inorganic acid dissociation reactions at high temperatures and pressures supports the validity and generality of the equations of state and the predictive algorithms. High temperature/pressure equilibrium constants can be predicted for reactions involving a wide variety of neutral aqueous species for which few or no experimental data are available at temperatures > 25°C. Present capabilities permit such predictions to be made for hydrothermal and magmatic conditions at pressures and temperatures to 5 kb and 1000°C.

Original languageEnglish (US)
Pages (from-to)2157-2183
Number of pages27
JournalGeochimica et Cosmochimica Acta
Volume53
Issue number9
DOIs
StatePublished - 1989
Externally publishedYes

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Transport properties
Thermodynamic properties
thermodynamics
Temperature
Equations of state
equation of state
temperature
Gases
Equilibrium constants
Electrolytes
electrolyte
liquid
calculation
Inorganic acids
gas
inorganic acid
Liquids
heat capacity
thermodynamic property
Phase equilibria

ASJC Scopus subject areas

  • Geochemistry and Petrology

Cite this

@article{45c4f4a573ca4d76a04cd306660298c9,
title = "Calculation of the thermodynamic and transport properties of aqueous species at high pressures and temperatures: Standard partial molal properties of inorganic neutral species",
abstract = "Consideration of interactions between neutral aqueous species and H2O dipoles in terms of effective Born coefficients permits extension of the revised HKF (Helgeson, Kirkham and Flowers, 1981) equations of state (Tanger and Helgeson, 1988) for the standard partial molal properties of ionic species at high pressures and temperatures to include inorganic gases, acids, and other neutral aqueous species. Correlation algorithms similar to those used to estimate equation of state parameters for ions and electrolytes (shock, and Helgeson, 1988) have also been developed for neutral aqueous species. Calculation of the standard partial molal thermodynamic properties of dissolved inorganic gases as well as other neutral aqueous species as a function of pressure and temperature indicates that the standard partial molal volume (V̄0), heat capacity (C̄0 p), and entropy (S̄0), together with the apparent standard partial molal enthalpy of formation (ΔH̄0) of many of these species in the liquid phase minimize with increasing temperature at PSAT * * PSAT represents pressures corresponding to liquid-vapor equilibrium for the system H2O, except at temperatures <100°C where it refers to the reference pressure of 1 bar. and approach ∞ at the critical point of H2O. In the case of other neutral aqueous species such as SiO2(aq), V ̄0, C ̄0 p, S ̄0, and Δ H ̄0 behave as functions of temperature and pressure like those of electrolytes in the liquid phase and maximize with increasing temperature at PSAT, approaching - ∞ at the critical point of H2O. Which of these types of behavior is exhibited by V ̄0, C ̄) p, S ̄0, and Δ H ̄0 for a given neutral aqueous species depends in part on the relative volatility of the aqueous species and the effect of the species on solvent dipole-dipole interaction. Close agreement between predicted and experimentally determined equilibrium constants for gas solubility and inorganic acid dissociation reactions at high temperatures and pressures supports the validity and generality of the equations of state and the predictive algorithms. High temperature/pressure equilibrium constants can be predicted for reactions involving a wide variety of neutral aqueous species for which few or no experimental data are available at temperatures > 25°C. Present capabilities permit such predictions to be made for hydrothermal and magmatic conditions at pressures and temperatures to 5 kb and 1000°C.",
author = "Everett Shock and Helgeson, {Harold C.} and Sverjensky, {Dimitri A.}",
year = "1989",
doi = "10.1016/0016-7037(89)90341-4",
language = "English (US)",
volume = "53",
pages = "2157--2183",
journal = "Geochmica et Cosmochimica Acta",
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TY - JOUR

T1 - Calculation of the thermodynamic and transport properties of aqueous species at high pressures and temperatures

T2 - Standard partial molal properties of inorganic neutral species

AU - Shock, Everett

AU - Helgeson, Harold C.

AU - Sverjensky, Dimitri A.

PY - 1989

Y1 - 1989

N2 - Consideration of interactions between neutral aqueous species and H2O dipoles in terms of effective Born coefficients permits extension of the revised HKF (Helgeson, Kirkham and Flowers, 1981) equations of state (Tanger and Helgeson, 1988) for the standard partial molal properties of ionic species at high pressures and temperatures to include inorganic gases, acids, and other neutral aqueous species. Correlation algorithms similar to those used to estimate equation of state parameters for ions and electrolytes (shock, and Helgeson, 1988) have also been developed for neutral aqueous species. Calculation of the standard partial molal thermodynamic properties of dissolved inorganic gases as well as other neutral aqueous species as a function of pressure and temperature indicates that the standard partial molal volume (V̄0), heat capacity (C̄0 p), and entropy (S̄0), together with the apparent standard partial molal enthalpy of formation (ΔH̄0) of many of these species in the liquid phase minimize with increasing temperature at PSAT * * PSAT represents pressures corresponding to liquid-vapor equilibrium for the system H2O, except at temperatures <100°C where it refers to the reference pressure of 1 bar. and approach ∞ at the critical point of H2O. In the case of other neutral aqueous species such as SiO2(aq), V ̄0, C ̄0 p, S ̄0, and Δ H ̄0 behave as functions of temperature and pressure like those of electrolytes in the liquid phase and maximize with increasing temperature at PSAT, approaching - ∞ at the critical point of H2O. Which of these types of behavior is exhibited by V ̄0, C ̄) p, S ̄0, and Δ H ̄0 for a given neutral aqueous species depends in part on the relative volatility of the aqueous species and the effect of the species on solvent dipole-dipole interaction. Close agreement between predicted and experimentally determined equilibrium constants for gas solubility and inorganic acid dissociation reactions at high temperatures and pressures supports the validity and generality of the equations of state and the predictive algorithms. High temperature/pressure equilibrium constants can be predicted for reactions involving a wide variety of neutral aqueous species for which few or no experimental data are available at temperatures > 25°C. Present capabilities permit such predictions to be made for hydrothermal and magmatic conditions at pressures and temperatures to 5 kb and 1000°C.

AB - Consideration of interactions between neutral aqueous species and H2O dipoles in terms of effective Born coefficients permits extension of the revised HKF (Helgeson, Kirkham and Flowers, 1981) equations of state (Tanger and Helgeson, 1988) for the standard partial molal properties of ionic species at high pressures and temperatures to include inorganic gases, acids, and other neutral aqueous species. Correlation algorithms similar to those used to estimate equation of state parameters for ions and electrolytes (shock, and Helgeson, 1988) have also been developed for neutral aqueous species. Calculation of the standard partial molal thermodynamic properties of dissolved inorganic gases as well as other neutral aqueous species as a function of pressure and temperature indicates that the standard partial molal volume (V̄0), heat capacity (C̄0 p), and entropy (S̄0), together with the apparent standard partial molal enthalpy of formation (ΔH̄0) of many of these species in the liquid phase minimize with increasing temperature at PSAT * * PSAT represents pressures corresponding to liquid-vapor equilibrium for the system H2O, except at temperatures <100°C where it refers to the reference pressure of 1 bar. and approach ∞ at the critical point of H2O. In the case of other neutral aqueous species such as SiO2(aq), V ̄0, C ̄0 p, S ̄0, and Δ H ̄0 behave as functions of temperature and pressure like those of electrolytes in the liquid phase and maximize with increasing temperature at PSAT, approaching - ∞ at the critical point of H2O. Which of these types of behavior is exhibited by V ̄0, C ̄) p, S ̄0, and Δ H ̄0 for a given neutral aqueous species depends in part on the relative volatility of the aqueous species and the effect of the species on solvent dipole-dipole interaction. Close agreement between predicted and experimentally determined equilibrium constants for gas solubility and inorganic acid dissociation reactions at high temperatures and pressures supports the validity and generality of the equations of state and the predictive algorithms. High temperature/pressure equilibrium constants can be predicted for reactions involving a wide variety of neutral aqueous species for which few or no experimental data are available at temperatures > 25°C. Present capabilities permit such predictions to be made for hydrothermal and magmatic conditions at pressures and temperatures to 5 kb and 1000°C.

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