TY - JOUR

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 L.

N1 - Funding Information:
The authors are indebted to V. Majer for sharing with us experimental results from his laboratory in advance of publication and to A. H. Harvey for his paper in advance of publication and for his comments on this paper. Thanks are due to two anonymous reviewers for their thoughtful comments and questions. The authors are indebted to J. M. H. Levelt Sengers for many informative discussions of critical point phenomena. This research was supported by the Department of Energy (DOE) under Grants Nos. DE-FG02-89ER-14080 and DE-FG02-92ER-14297.

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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U2 - 10.1016/S0016-7037(00)00390-2

DO - 10.1016/S0016-7037(00)00390-2

M3 - Article

AN - SCOPUS:0033811383

VL - 64

SP - 2779

EP - 2795

JO - Geochmica et Cosmochimica Acta

JF - Geochmica et Cosmochimica Acta

SN - 0016-7037

IS - 16

ER -