TY - JOUR
T1 - Inorganic species in geologic fluids
T2 - Correlations among standard molal thermodynamic properties of aqueous ions and hydroxide complexes
AU - Shock, Everett L.
AU - Sassani, David C.
AU - Willis, Marc
AU - Sverjensky, Dimitri A.
N1 - Funding Information:
Acknowledgments--We wish to thanks everacl olleaguefso r helpful discussiondsu ringt hec ourseo f this studyi ncludingT om McCol-lom, Mitch Schulte,J ill PasterisJ,. K. B6hlke, Harold Helgeson, Vitalii PokravskiiE, ric Oelkers,J amesW . JohnsonW, illiamMur-phy, JohnsonH aas,Carla Koretsky,a ndLaura Wetzel.R ho plots usedi n this studyw ereg eneratebdy RebeccaL loyd with help from Tom McCollom,J onathanIc enhowerM, itchS chultea, ndB ill Moss. Considerabltee chnicaal ssistancwea s suppliedb y RachelL indvall, JenniferT hieme,P attyDuBois, Bill Winston,D ee Becker,C arla KoretskyH, eidiB etz,S tephanS chmidtD, ougL arowe,G avinC han, Jenny Yoo, BarbaraW inston,a ndM ichelleM organ,a ndis greatly appreciatedC.a refulr eviewsa nd commentbs y Don Palmer,J im JohnsonJ,e ff SeewaldG, regA ndersona, ndE ric Oelkersw ereh elp-ful in revisingt hem anuscripItn. additionw, e wantt o thankJ amie Hovey,J acquesS chotta, ndD aveW esolowskfio r generouslsyh aring resultso f theire xperimentwalo rk in advanceo f publicationT.h is researchw as funded by NSF grantsE AR-8905018a nd OCE-9220337a, ndDOE grantD E-FGO2-92ER1429t7o ELS, and NSF grantsE AR-872251E, AR-9526623a, nd OCE-9200208a, ndDOE grantD EFG-0296ER-1461t6o DAS. This is GEOPIG Contribution 34.
PY - 1997/3
Y1 - 1997/3
N2 - Correlations among experimentally determined standard partial molal thermodynamic properties of inorganic aqueous species at 25°C and 1 bar allow estimates of these properties for numerous monatomic cations and anions, polyatomic anions, oxyanions, acid oxyanions, neutral oxy-acid species, dissolved gases, and hydroxide complexes of metal cations. Combined with correlations among parameters in the revised Helgeson-Kirkham-Flowers (HKF) equation of state (Shock et al., 1992), these estimates permit predictions of standard partial molal volumes (V̄°), heat capacities (C̄°P), and entropies (S̄°), as well as apparent standard partial molal enthalpies (ΔH̄°P,T) and Gibbs free energies (ΔḠ°P,T) of formation to 1000°C and 5 kb for hundreds of inorganic aqueous species of interest in geochemistry. Data and parameters for more than 300 inorganic aqueous species are presented. Close agreement between calculated and experimentally determined equilibrium constants for acid dissociation reactions and cation hydrolysis reactions supports the generality and validity of these predictive methods. These data facilitate the calculation of the speciation of major, minor, and trace elements in hydrothermal and metamorphic fluids throughout most of the crust of the Earth.
AB - Correlations among experimentally determined standard partial molal thermodynamic properties of inorganic aqueous species at 25°C and 1 bar allow estimates of these properties for numerous monatomic cations and anions, polyatomic anions, oxyanions, acid oxyanions, neutral oxy-acid species, dissolved gases, and hydroxide complexes of metal cations. Combined with correlations among parameters in the revised Helgeson-Kirkham-Flowers (HKF) equation of state (Shock et al., 1992), these estimates permit predictions of standard partial molal volumes (V̄°), heat capacities (C̄°P), and entropies (S̄°), as well as apparent standard partial molal enthalpies (ΔH̄°P,T) and Gibbs free energies (ΔḠ°P,T) of formation to 1000°C and 5 kb for hundreds of inorganic aqueous species of interest in geochemistry. Data and parameters for more than 300 inorganic aqueous species are presented. Close agreement between calculated and experimentally determined equilibrium constants for acid dissociation reactions and cation hydrolysis reactions supports the generality and validity of these predictive methods. These data facilitate the calculation of the speciation of major, minor, and trace elements in hydrothermal and metamorphic fluids throughout most of the crust of the Earth.
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U2 - 10.1016/S0016-7037(96)00339-0
DO - 10.1016/S0016-7037(96)00339-0
M3 - Article
C2 - 11541225
AN - SCOPUS:0030879141
SN - 0016-7037
VL - 61
SP - 907
EP - 950
JO - Geochimica et Cosmochimica Acta
JF - Geochimica et Cosmochimica Acta
IS - 5
ER -