TY - JOUR
T1 - The temperature dependence of the standard-state thermodynamic properties of aqueous nonelectrolytes
AU - Schulte, Mitchell D.
AU - Shock, Everett L.
AU - Wood, Robert H.
N1 - Funding Information:
We are pleased to be able to contribute this paper in honor of Professor Harold Helgeson’s 70th birthday. This study benefited from numerous discussions with Vladimir Majer, Marek Obšil, Jan Amend, and Dimitri Sverjensky and was funded by Department of Energy Grant Numbers DE-FG02-92ER14297 to ELS and DE-FG02-89ER 14080 to RHW. We thank Lubosh Hnědkovský, Andrei Sharygin, and Vladimir Majer for data and manuscripts in advance of publication and Katharina Lodders for advice on PH 3 . Comments and suggestions by Vladimir Majer, Eric Oelkers, and an anonymous reviewer greatly improved the quality of this manuscript. This is GEOPIG Contribution No. 131.
PY - 2001
Y1 - 2001
N2 - Recent experimental studies of the standard-state heat capacities of aqueous nonelectrolytes at high temperatures make it possible to test predictions made with theoretical equations of state and correlation algorithms. Existing predictive methods are qualitatively correct and produce quantitative results that are in reasonable agreement with the new experimental data at temperature ≤ 350°C, but much better results are possible using new data. Regression of the new data for CO2(aq). H2S(aq), CH4(aq), NH3(aq), and SO2(aq) leads to revised parameters for the revised Helgeson-Kirkham-Flowers (HKF) equation of state. New correlations based on these parameters allow revised regressions of older data for Xe(aq), Ar(aq), and C2H4(aq) and lead to new predictions for several other aqueous nonelectrolytes. These predictions are tested against experimentally determined equilibrium constants for reactions involving several other aqueous nonelectrolytes, including He(aq), Ne(aq), Kr(aq), Rn(aq), H2(aq), N2(aq), O2(aq), and CO(aq). The correlations developed are used to make predictions for a variety of other aqueous nonelectrolytes, allowing incorporation of these species into models of geochemical processes.
AB - Recent experimental studies of the standard-state heat capacities of aqueous nonelectrolytes at high temperatures make it possible to test predictions made with theoretical equations of state and correlation algorithms. Existing predictive methods are qualitatively correct and produce quantitative results that are in reasonable agreement with the new experimental data at temperature ≤ 350°C, but much better results are possible using new data. Regression of the new data for CO2(aq). H2S(aq), CH4(aq), NH3(aq), and SO2(aq) leads to revised parameters for the revised Helgeson-Kirkham-Flowers (HKF) equation of state. New correlations based on these parameters allow revised regressions of older data for Xe(aq), Ar(aq), and C2H4(aq) and lead to new predictions for several other aqueous nonelectrolytes. These predictions are tested against experimentally determined equilibrium constants for reactions involving several other aqueous nonelectrolytes, including He(aq), Ne(aq), Kr(aq), Rn(aq), H2(aq), N2(aq), O2(aq), and CO(aq). The correlations developed are used to make predictions for a variety of other aqueous nonelectrolytes, allowing incorporation of these species into models of geochemical processes.
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U2 - 10.1016/S0016-7037(01)00717-7
DO - 10.1016/S0016-7037(01)00717-7
M3 - Article
AN - SCOPUS:0035194001
SN - 0016-7037
VL - 65
SP - 3919
EP - 3930
JO - Geochimica et Cosmochimica Acta
JF - Geochimica et Cosmochimica Acta
IS - 21
ER -