Metal-organic complexes in geochemical processes: Estimation of standard partial molal thermodynamic properties of aqueous complexes between metal cations and monovalent organic acid ligands at high pressures and temperatures

doi:10.1016/0016-7037(95)00058-8

Geochimica et Cosmochimica Acta

Volume 59, Issue 8, April 1995, Pages 1497-1532

https://doi.org/10.1016/0016-7037(95)00058-8 Get rights and content

Abstract

Regression of standard state equilibrium constants with the revised Helgeson-Kirkham-Flowers (HKF) equation of state allows evaluation of standard partial molal entropies ( $S$ ^o) of aqueous metal-organic complexes involving monovalent organic acid ligands. These values of $S$ ^o provide the basis for correlations that can be used, together with correlation algorithms among standard partial molal properties of aqueous complexes and equation-of-state parameters, to estimate thermodynamic properties including equilibrium constants for complexes between aqueous metals and several monovalent organic acid ligands at the elevated pressures and temperatures of many geochemical processes which involve aqueous solutions. Data, parameters, and estimates are given for 270 formate, propanoate, n-butanoate, n-pentanoate, glycolate, lactate, glycinate, and alanate complexes, and a consistent algorithm is provided for making other estimates. Standard partial molal entropies of association ( $Δ − S_{r}^{o}$ ) for metal-monovalent organic acid ligand complexes fall into at least two groups dependent upon the type of functional groups present in the ligand. It is shown that isothermal correlations among equilibrium constants for complex formation are consistent with one another and with similar correlations for inorganic metal-ligand complexes. Additional correlations allow estimates of standard partial molal Gibbs free energies of association at 25°C and 1 bar which can be used in cases where no experimentally derived values are available.

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^∗: Present address: Department of Earth and Planetary Sciences, The Johns Hopkins University, Baltimore, MD 21218, USA.

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ArticleMetal-organic complexes in geochemical processes: Estimation of standard partial molal thermodynamic properties of aqueous complexes between metal cations and monovalent organic acid ligands at high pressures and temperatures

Abstract

J. Inorg. Nucl. Chem.

Geochim. Cosmochim. Acta

Geochim. Cosmochim. Acta

J. Inorg. Nucl. Chem.

Geochim. Cosmochim. Acta

Inorg. Chim. Acta

Inorg. Nucl. Chem. Lett.

J. Inorg. Nucl. Chem.

J. Inorg. Nucl. Chem.

Geochim. Cosmochim. Acta

Geochim. Cosmochim. Acta

Appl. Geochim.

Geochim. Cosmochim. Acta

Quantitative studies of the avidity of naturally occurring substances for trace metals

Biochemical J.

Formation constants and enthalpy and entropy values for the association of H+ and Cu2+ with glycinate and phenylalanate ions in aqueous solution at 10, 25 and 40°

Inorg. Chem.

Formation constant, enthalpy, and entropy values for the association of nickel(II) ion with glycinate, alanate, and phenylalanate ions at 10, 25, and 40°

Inorg. Chem.

Ion-association constants of some acetates by pH (glass electrode) measurements

J. Chem. Soc.

Dissociation constants of some ytterbium ion-pairs from cation-exchange resin studies

J. Chem. Soc.

The study of some ion-pairs by spectrophotometry

Discussions of the Faraday Society

Complex formation by beryllium with glycollic, lactic, and mandelic acids

Russ. J. Inorg. Chem.

Computer simulation of metal-ion equilibria in biofluids. Part 2. Formation constants for zinc (II)-citrate-cysteinate binary and ternary complexes and improved models of low-molecular-weight zinc species in blood plasma

J. Chem. Soc. Dalton Trans.

Thermodynamics of ion association transition-metal β-alanine and glycine complexes

J. Chem. Eng. Data

Thermodynamics of ion association. Part XI. Some transition-metal glycine salts

J. Chem. Soc.

The solubility of BaCO3(cr) witherite in CO2H2O solutions between 0 and 90°C evaluation of the association constants of BaHCO3+ (aq) and BaCO30(aq) between 5 and 80°C, and a preliminary evaluation of the thermodynamic properties of Ba2+(aq)

Geochim. Cosmochim. Acta

Complex formation between carboxylic acids and divalent metal cations

J. Amer. Chem. Soc.

Thermodynamic functions and stability constants of TI(III) glycollates

J. Ind. Chem. Soc.

Thermodynamic study of Ti (III) complexes with α-hydroxy acids

Vijnana Parishad Anusandhan Patrika

Studies in some amino-acid chelates: Part I

J. Ind. Chem. Soc.

Ionic equilibria in aqueous solutions of cadmium acetate and the related thermodynamic functions

J. Ind. Chem. Soc.

Dissociation constants of the alkaline-earth salts of some monocarboxylic acids

J. Chem. Soc.

On the possibility of determining the thermodynamic parameters for the formation of weak complexes using a simple model for the dependence on ionic strength of activity coefficients: Na+, K+, and Ca2+ complexes of low molecular weight ligands in aqueous solution

J. Chem. Soc. Dalton Trans.

The extent of dissociation of salts in water. Part IV. Some calcium salts of organic acids

J. Chem. Soc.

The extent of dissociation of salts in water. Part XII. Calcium salts of some amino-acids and dipeptides

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The influence of mixed solvents on the dissociation constant of silver acetate

J. Chem. Soc.

E.M.F. studies of electrolytic dissociation. Part 5. Some glycollates in water

Trans. Faraday Soc.

E.M.F. Studies of electrolytic dissociation. Part 6. Some lactates in water

Trans. Faraday Soc.

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Quim. Anal.

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Article
Metal-organic complexes in geochemical processes: Estimation of standard partial molal thermodynamic properties of aqueous complexes between metal cations and monovalent organic acid ligands at high pressures and temperatures

Formation constants and enthalpy and entropy values for the association of H⁺ and Cu²⁺ with glycinate and phenylalanate ions in aqueous solution at 10, 25 and 40°

The solubility of BaCO₃(cr) witherite in CO₂H₂O solutions between 0 and 90°C evaluation of the association constants of BaHCO₃⁺ (aq) and BaCO₃⁰(aq) between 5 and 80°C, and a preliminary evaluation of the thermodynamic properties of Ba²⁺(aq)

On the possibility of determining the thermodynamic parameters for the formation of weak complexes using a simple model for the dependence on ionic strength of activity coefficients: Na⁺, K⁺, and Ca²⁺ complexes of low molecular weight ligands in aqueous solution