Infinite dilution partial molar properties of aqueous solutions of nonelectrolytes. II. Equations for the standard thermodynamic functions of hydration of volatile nonelectrolytes over wide ranges of conditions including subcritical temperatures

Andrey V. Plyasunov, John P. O'Connell, Robert H. Wood, Everett Shock

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Abstract

The volumetric equation proposed previously (Plyasunov et al., 2000), for estimating the infinite dilution Gibbs energy of hydration of volatile nonelectrolytes at temperatures exceeding the critical temperature of pure water, T(c), is extended to subcritical temperatures. The basis for the extension without inclusion of new fitting parameters besides the experimental values of the thermodynamic functions of hydration at 298.15 K, 0.1 MPa, is an auxiliary function, Δ(h)Cp0(T, P(r)), for the variation of the infinite dilution partial molar heat capacity of hydration of a solute in liquid-like water between temperatures T = 273.15 K and T = T(s) = 658 K along the isobar P(r) = 28 MPa. The analytical form of Δ(h)Cp0(T, P(r)) was found by globally fitting all available data for the seven best-studied solutes (CH4, CO2, H2S, NH3, Ar, Xe, and C2H4). Four constraints were used to determine the values of four terms of the Δ(h)Cp0(T, P(r)) function: the numerical values of the temperature increments between T = 298.15 K and T = T(s) = 658 K for the Gibbs energy and the enthalpy of hydration, and numerical value of the heat capacity at T(s) and at 298.15 K, all at the selected isobar P(r). This approach, in combination with the volumetric equation, may be used to describe and predict all the infinite dilution thermodynamic functions of hydration for nonelectrolytes over extremely wide ranges of temperature and pressure. The model allows calculation of the standard state partial molar properties, including the Gibbs energy of aqueous solutes in a single framework for conditions from high-temperature magmatic processes through hydrothermal phenomena to low-temperature conditions of hypergenesis. Copyright (C) 2000 Elsevier Science Ltd.

Original languageEnglish (US)
Pages (from-to)2779-2795
Number of pages17
JournalGeochimica et Cosmochimica Acta
Volume64
Issue number16
DOIs
StatePublished - 2000
Externally publishedYes

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hydration
Hydration
Dilution
dilution
aqueous solution
thermodynamics
Thermodynamics
solute
heat capacity
Gibbs free energy
temperature
hydrothermal phenomena
Temperature
energy
Specific heat
enthalpy
water temperature
Water
liquid
Enthalpy

ASJC Scopus subject areas

  • Geochemistry and Petrology

Cite this

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title = "Infinite dilution partial molar properties of aqueous solutions of nonelectrolytes. II. Equations for the standard thermodynamic functions of hydration of volatile nonelectrolytes over wide ranges of conditions including subcritical temperatures",
abstract = "The volumetric equation proposed previously (Plyasunov et al., 2000), for estimating the infinite dilution Gibbs energy of hydration of volatile nonelectrolytes at temperatures exceeding the critical temperature of pure water, T(c), is extended to subcritical temperatures. The basis for the extension without inclusion of new fitting parameters besides the experimental values of the thermodynamic functions of hydration at 298.15 K, 0.1 MPa, is an auxiliary function, Δ(h)Cp0(T, P(r)), for the variation of the infinite dilution partial molar heat capacity of hydration of a solute in liquid-like water between temperatures T = 273.15 K and T = T(s) = 658 K along the isobar P(r) = 28 MPa. The analytical form of Δ(h)Cp0(T, P(r)) was found by globally fitting all available data for the seven best-studied solutes (CH4, CO2, H2S, NH3, Ar, Xe, and C2H4). Four constraints were used to determine the values of four terms of the Δ(h)Cp0(T, P(r)) function: the numerical values of the temperature increments between T = 298.15 K and T = T(s) = 658 K for the Gibbs energy and the enthalpy of hydration, and numerical value of the heat capacity at T(s) and at 298.15 K, all at the selected isobar P(r). This approach, in combination with the volumetric equation, may be used to describe and predict all the infinite dilution thermodynamic functions of hydration for nonelectrolytes over extremely wide ranges of temperature and pressure. The model allows calculation of the standard state partial molar properties, including the Gibbs energy of aqueous solutes in a single framework for conditions from high-temperature magmatic processes through hydrothermal phenomena to low-temperature conditions of hypergenesis. Copyright (C) 2000 Elsevier Science Ltd.",
author = "Plyasunov, {Andrey V.} and O'Connell, {John P.} and Wood, {Robert H.} and Everett Shock",
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T1 - Infinite dilution partial molar properties of aqueous solutions of nonelectrolytes. II. Equations for the standard thermodynamic functions of hydration of volatile nonelectrolytes over wide ranges of conditions including subcritical temperatures

AU - Plyasunov, Andrey V.

AU - O'Connell, John P.

AU - Wood, Robert H.

AU - Shock, Everett

PY - 2000

Y1 - 2000

N2 - The volumetric equation proposed previously (Plyasunov et al., 2000), for estimating the infinite dilution Gibbs energy of hydration of volatile nonelectrolytes at temperatures exceeding the critical temperature of pure water, T(c), is extended to subcritical temperatures. The basis for the extension without inclusion of new fitting parameters besides the experimental values of the thermodynamic functions of hydration at 298.15 K, 0.1 MPa, is an auxiliary function, Δ(h)Cp0(T, P(r)), for the variation of the infinite dilution partial molar heat capacity of hydration of a solute in liquid-like water between temperatures T = 273.15 K and T = T(s) = 658 K along the isobar P(r) = 28 MPa. The analytical form of Δ(h)Cp0(T, P(r)) was found by globally fitting all available data for the seven best-studied solutes (CH4, CO2, H2S, NH3, Ar, Xe, and C2H4). Four constraints were used to determine the values of four terms of the Δ(h)Cp0(T, P(r)) function: the numerical values of the temperature increments between T = 298.15 K and T = T(s) = 658 K for the Gibbs energy and the enthalpy of hydration, and numerical value of the heat capacity at T(s) and at 298.15 K, all at the selected isobar P(r). This approach, in combination with the volumetric equation, may be used to describe and predict all the infinite dilution thermodynamic functions of hydration for nonelectrolytes over extremely wide ranges of temperature and pressure. The model allows calculation of the standard state partial molar properties, including the Gibbs energy of aqueous solutes in a single framework for conditions from high-temperature magmatic processes through hydrothermal phenomena to low-temperature conditions of hypergenesis. Copyright (C) 2000 Elsevier Science Ltd.

AB - The volumetric equation proposed previously (Plyasunov et al., 2000), for estimating the infinite dilution Gibbs energy of hydration of volatile nonelectrolytes at temperatures exceeding the critical temperature of pure water, T(c), is extended to subcritical temperatures. The basis for the extension without inclusion of new fitting parameters besides the experimental values of the thermodynamic functions of hydration at 298.15 K, 0.1 MPa, is an auxiliary function, Δ(h)Cp0(T, P(r)), for the variation of the infinite dilution partial molar heat capacity of hydration of a solute in liquid-like water between temperatures T = 273.15 K and T = T(s) = 658 K along the isobar P(r) = 28 MPa. The analytical form of Δ(h)Cp0(T, P(r)) was found by globally fitting all available data for the seven best-studied solutes (CH4, CO2, H2S, NH3, Ar, Xe, and C2H4). Four constraints were used to determine the values of four terms of the Δ(h)Cp0(T, P(r)) function: the numerical values of the temperature increments between T = 298.15 K and T = T(s) = 658 K for the Gibbs energy and the enthalpy of hydration, and numerical value of the heat capacity at T(s) and at 298.15 K, all at the selected isobar P(r). This approach, in combination with the volumetric equation, may be used to describe and predict all the infinite dilution thermodynamic functions of hydration for nonelectrolytes over extremely wide ranges of temperature and pressure. The model allows calculation of the standard state partial molar properties, including the Gibbs energy of aqueous solutes in a single framework for conditions from high-temperature magmatic processes through hydrothermal phenomena to low-temperature conditions of hypergenesis. Copyright (C) 2000 Elsevier Science Ltd.

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