An Experimental Study of the Solubility of Rare Earth Chloride Salts (La, Nd, Er) in HCl Bearing Water Vapor from 350 – 425 °C

Alcorn, Christopher Darrell; Velizhanin, Kirill A.; Strzelecki, Andrew Charles; Nisbet, Haylea Dawn; Roback, Robert Clifford; Currier, Robert Patrick; Migdissov, Artaches

doi:10.1016/j.gca.2021.06.011

Title: An Experimental Study of the Solubility of Rare Earth Chloride Salts (La, Nd, Er) in HCl Bearing Water Vapor from 350 – 425 °C

Journal Article · Tue Jun 15 00:00:00 UTC 2021 · Geochimica et Cosmochimica Acta

DOI: https://doi.org/10.1016/j.gca.2021.06.011 · OSTI ID:1804363

^[1];

^[1]; Strzelecki, Andrew Charles ^[1];

^[1];

^[1]

Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

In this work, the solubilities of the rare earth chlorides REECl₃, where REE = (La, Nd, Er), were measured in HCl bearing water vapor from 350 – 425°C with water partial pressures ranging from 8 – 170 bar. Solubility data were fit to the Pitzer-Pabalan quasi-chemical model in order to extract thermodynamic parameters for the formation of the gaseous REE-chloride-water clusters REECl₃(H₂O)_n. The data show that the solubility of the REE chlorides are orders of magnitude higher than salts such as NaCl or CuCl at low water fugacities, despite their sublimation energies being substantially higher. This enhanced solubility is likely due to the high enthalpy associated with binding a single water molecule to form the species REECl₃(H₂O), with derived enthalpies ranging from –378 to –465 kJ/mol. Addition of further water molecules to form higher order clusters (n > 1) involves enthalpy changes of ~ -20 kJ/mol, and are in effect thermodynamically suppressed over the temperature range 350 – 425°C. Despite the enhanced solubility of small REECl₃ water clusters, simulations of boiling processes demonstrate that the REE show highly conservative behavior, partitioning strongly into the dense aqueous phase. Not surprisingly, the presence of phosphates in the system makes this effect even more pronounced, completely immobilizing the REE. This would reduce transport in both the vapor and aqueous phase to negligible levels. However, we suggest that vapor phase transport of the REE may play a significant role in systems having a relatively low partial pressure of water (below the saturation point), where the relatively high stability of the first hydrated REE chloride clusters (REECl₃(H₂O) and REECl₃(H₂O)₂) will give a preference for gas transport of the REE relative to other elements. This can likely happen in systems involving a gas/melt exchange in fumarolic exhalations, where water vapor discharges at relatively low (close to atmospheric) pressures.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE; USDOE Laboratory Directed Research and Development (LDRD) Program

Grant/Contract Number:: 89233218CNA000001

OSTI ID:: 1804363

Report Number(s):: LA-UR--20-29341

Journal Information:: Geochimica et Cosmochimica Acta, Journal Name: Geochimica et Cosmochimica Acta Vol. 330; ISSN 0016-7037

Publisher:: Elsevier; The Geochemical Society; The Meteoritical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (45)

PRSV: An improved peng-Robinson equation of state for pure compounds and mixtures Stryjek, R.; Vera, J. H. The Canadian Journal of Chemical Engineering, Vol. 64, Issue 2 https://doi.org/10.1002/cjce.5450640224	journal	April 1986
REE composition of an aqueous magmatic fluid: A fluid inclusion study from the Capitan Pluton, New Mexico, U.S.A. Banks, D. A.; Yardley, B. W. D.; Campbell, A. R. Chemical Geology, Vol. 113, Issue 3-4 https://doi.org/10.1016/0009-2541(94)90070-1	journal	April 1994
The system NaCl-H2O: Relations of vapor-liquid near the critical temperature of water and of vapor-liquid-halite from 300° to 500°C Bischoff, James L.; Rosenbauer, Robert J.; Pitzer, Kenneth S. Geochimica et Cosmochimica Acta, Vol. 50, Issue 7 https://doi.org/10.1016/0016-7037(86)90317-0	journal	July 1986
Thermodynamics of NaCl in steam Pitzer, Kenneth S.; Pabalan, Roberto T. Geochimica et Cosmochimica Acta, Vol. 50, Issue 7 https://doi.org/10.1016/0016-7037(86)90318-2	journal	July 1986
Phase relations in the system NaCl-KCl-H2O. III: Solubilities of halite in vapor-saturated liquids above 445°C and redetermination of phase equilibrium properties in the system NaCl-H2O to 1000°C and 1500 bars Chou, I-Ming Geochimica et Cosmochimica Acta, Vol. 51, Issue 7 https://doi.org/10.1016/0016-7037(87)90185-2	journal	July 1987
Liquid-vapor relations in the critical region of the system NaCl-H2O from 380 to 415°C: A refined determination of the critical point and two-phase boundary of seawater Bischoff, James L.; Rosenbauer, Robert J. Geochimica et Cosmochimica Acta, Vol. 52, Issue 8 https://doi.org/10.1016/0016-7037(88)90192-5	journal	August 1988
Calculation of activity coefficients and degrees of formation of neutral ion pairs in supercritical electrolyte solutions Oelkers, Eric H.; Helgeson, Harold C. Geochimica et Cosmochimica Acta, Vol. 55, Issue 5 https://doi.org/10.1016/0016-7037(91)90303-M	journal	May 1991
Rare earth elements in hydrothermal systems: Estimates of standard partial molal thermodynamic properties of aqueous complexes of the rare earth elements at high pressures and temperatures Haas, Johnson R.; Shock, Everett L.; Sassani, David C. Geochimica et Cosmochimica Acta, Vol. 59, Issue 21 https://doi.org/10.1016/0016-7037(95)00314-P	journal	November 1995
SUPCRT92: A software package for calculating the standard molal thermodynamic properties of minerals, gases, aqueous species, and reactions from 1 to 5000 bar and 0 to 1000°C Johnson, James W.; Oelkers, Eric H.; Helgeson, Harold C. Computers & Geosciences, Vol. 18, Issue 7 https://doi.org/10.1016/0098-3004(92)90029-Q	journal	August 1992
Prediction of ternary vapor-liquid equilibria with the PRSV equation of state Sandoval, R.; Wilczek-Vera, G.; Vera, J. H. Fluid Phase Equilibria, Vol. 52 https://doi.org/10.1016/0378-3812(89)80318-8	journal	December 1989
Solubility of sodium chloride and sulfate in sub- and supercritical water vapor from 450–550°C and 100–250 bar Armellini, Fred J.; Tester, Jefferson W. Fluid Phase Equilibria, Vol. 84 https://doi.org/10.1016/0378-3812(93)85120-B	journal	April 1993
An experimental study of the stability of copper chloride complexes in water vapor at elevated temperatures and pressures Archibald, S. M.; Migdisov, A. A.; Williams-Jones, A. E. Geochimica et Cosmochimica Acta, Vol. 66, Issue 9 https://doi.org/10.1016/S0016-7037(01)00867-5	journal	May 2002
Experimental study of arsenic speciation in vapor phase to 500°C: implications for As transport and fractionation in low-density crustal fluids and volcanic gases Pokrovski, Gleb S.; Zakirov, Ildar V.; Roux, Jacques Geochimica et Cosmochimica Acta, Vol. 66, Issue 19 https://doi.org/10.1016/S0016-7037(02)00946-8	journal	October 2002
Partitioning of rare earth elements, yttrium, and some major elements among source rocks, liquid and vapor of Larderello-Travale geothermal field, Tuscany (Central Italy) Möller, P.; Dulski, P.; Morteani, G. Geochimica et Cosmochimica Acta, Vol. 67, Issue 2 https://doi.org/10.1016/S0016-7037(02)01054-2	journal	January 2003
Inorganic species in geologic fluids: Correlations among standard molal thermodynamic properties of aqueous ions and hydroxide complexes Shock, Everett L.; Sassani, David C.; Willis, Marc Geochimica et Cosmochimica Acta, Vol. 61, Issue 5 https://doi.org/10.1016/S0016-7037(96)00339-0	journal	March 1997
Prediction of the thermodynamic properties of aqueous metal complexes to 1000°C and 5 kb Sverjensky, D. A.; Shock, E. L.; Helgeson, H. C. Geochimica et Cosmochimica Acta, Vol. 61, Issue 7 https://doi.org/10.1016/S0016-7037(97)00009-4	journal	April 1997
An experimental study of cassiterite solubility in HCl-bearing water vapour at temperatures up to 350 °C. Implications for tin ore formation Migdisov, Art A.; Williams-Jones, A. E. Chemical Geology, Vol. 217, Issue 1-2 https://doi.org/10.1016/j.chemgeo.2004.11.018	journal	April 2005
Hydrothermal transport, deposition, and fractionation of the REE: Experimental data and thermodynamic calculations Migdisov, A.; Williams-Jones, A. E.; Brugger, J. Chemical Geology, Vol. 439 https://doi.org/10.1016/j.chemgeo.2016.06.005	journal	November 2016
A review of the coordination chemistry of hydrothermal systems, or do coordination changes make ore deposits? Brugger, Joël; Liu, Weihua; Etschmann, Barbara Chemical Geology, Vol. 447 https://doi.org/10.1016/j.chemgeo.2016.10.021	journal	December 2016
The effect of sulfur on vapor–liquid fractionation of metals in hydrothermal systems Pokrovski, Gleb S.; Borisova, Anastassia Yu.; Harrichoury, Jean-Claude Earth and Planetary Science Letters, Vol. 266, Issue 3-4 https://doi.org/10.1016/j.epsl.2007.11.023	journal	February 2008
Rigorous analysis of non-ideal solubility of sodium and copper chlorides in water vapor using Pitzer-Pabalan model Velizhanin, K. A.; Alcorn, C. D.; Migdisov, A. A. Fluid Phase Equilibria, Vol. 522 https://doi.org/10.1016/j.fluid.2020.112731	journal	November 2020
The solubility and speciation of molybdenum in water vapour at elevated temperatures and pressures: Implications for ore genesis Rempel, K. U.; Migdisov, A. A.; Williams-Jones, A. E. Geochimica et Cosmochimica Acta, Vol. 70, Issue 3 https://doi.org/10.1016/j.gca.2005.09.013	journal	February 2006
The solubility of molybdenum dioxide and trioxide in HCl-bearing water vapour at 350°C and pressures up to 160 bars Rempel, K. U.; Williams-Jones, A. E.; Migdisov, A. A. Geochimica et Cosmochimica Acta, Vol. 72, Issue 13 https://doi.org/10.1016/j.gca.2008.04.015	journal	July 2008
An experimental study of the solubility and speciation of the Rare Earth Elements (III) in fluoride- and chloride-bearing aqueous solutions at temperatures up to 300°C Migdisov, Art. A.; Williams-Jones, A. E.; Wagner, T. Geochimica et Cosmochimica Acta, Vol. 73, Issue 23 https://doi.org/10.1016/j.gca.2009.08.023	journal	December 2009
An experimental study of the elemental and isotopic fractionation of copper between aqueous vapour and liquid to 450°C and 400bar in the CuCl–NaCl–H2O and CuCl–NaHS–NaCl–H2O systems Rempel, Kirsten U.; Liebscher, Axel; Meixner, Anette Geochimica et Cosmochimica Acta, Vol. 94 https://doi.org/10.1016/j.gca.2012.06.028	journal	October 2012
A predictive model for metal transport of silver chloride by aqueous vapor in ore-forming magmatic-hydrothermal systems Migdisov, Art. A.; Williams-Jones, A. E. Geochimica et Cosmochimica Acta, Vol. 104 https://doi.org/10.1016/j.gca.2012.11.020	journal	March 2013
An experimental study of the transport of gold through hydration of AuCl in aqueous vapour and vapour-like fluids Hurtig, Nicole C.; Williams-Jones, Anthony E. Geochimica et Cosmochimica Acta, Vol. 127 https://doi.org/10.1016/j.gca.2013.11.029	journal	February 2014
A predictive model for the transport of copper by HCl-bearing water vapour in ore-forming magmatic-hydrothermal systems: Implications for copper porphyry ore formation Migdisov, Art. A.; Bychkov, A. Yu.; Williams-Jones, A. E. Geochimica et Cosmochimica Acta, Vol. 129 https://doi.org/10.1016/j.gca.2013.12.024	journal	March 2014
Fractionation of REE, U, and Th in natural ore-forming hydrothermal systems: Thermodynamic modeling Migdisov, A.; Guo, X.; Nisbet, H. The Journal of Chemical Thermodynamics, Vol. 128 https://doi.org/10.1016/j.jct.2018.08.032	journal	January 2019
Vapour transport of rare earth elements (REE) in volcanic gas: Evidence from encrustations at Oldoinyo Lengai Gilbert, C. D.; Williams-Jones, A. E. Journal of Volcanology and Geothermal Research, Vol. 176, Issue 4 https://doi.org/10.1016/j.jvolgeores.2008.05.003	journal	October 2008
Case for covalent bonding in lanthanide trihalides Myers, Clifford E. Inorganic Chemistry, Vol. 14, Issue 1 https://doi.org/10.1021/ic50143a044	journal	January 1975
Structural and Thermochemical ab Initio Studies of Lanthanide Trihalide Molecules with Pseudopotentials Joubert, Laurent; Picard, Gérard; Legendre, Jean-Jacques Inorganic Chemistry, Vol. 37, Issue 8 https://doi.org/10.1021/ic970350v	journal	March 1998
Calculation of Electronic Spectra of Hydrated Ln(III) Ions within the INDO/S-CI Approach Kotzian, Manfred; Fox, Thomas; Roesch, Notker The Journal of Physical Chemistry, Vol. 99, Issue 2 https://doi.org/10.1021/j100002a023	journal	January 1995
Solubility of sodium chloride in dry steam Galobardes, Javier F.; Van Hare, David R.; Rogers, Lockhart B. Journal of Chemical & Engineering Data, Vol. 26, Issue 4 https://doi.org/10.1021/je00026a004	journal	October 1981
Extension of Computational Chemistry to the Study of Lanthanide(III) Ions in Aqueous Solution: Implementation and Validation of a Continuum Solvent Approach Cosentino, U.; Villa, A.; Pitea, D. The Journal of Physical Chemistry B, Vol. 104, Issue 33 https://doi.org/10.1021/jp994022n	journal	August 2000
The roles of 4f- and 5f-orbitals in bonding: a magnetochemical, crystal field, density functional theory, and multi-reference wavefunction study Lukens, W. W.; Speldrich, M.; Yang, P. Dalton Transactions, Vol. 45, Issue 28 https://doi.org/10.1039/C6DT00634E	journal	January 2016
The IAPWS Formulation 1995 for the Thermodynamic Properties of Ordinary Water Substance for General and Scientific Use Wagner, W.; Pruß, A. Journal of Physical and Chemical Reference Data, Vol. 31, Issue 2 https://doi.org/10.1063/1.1461829	journal	June 2002
Ion product of water substance, 0–1000 °C, 1–10,000 bars New International Formulation and its background Marshall, William L.; Franck, E. U. Journal of Physical and Chemical Reference Data, Vol. 10, Issue 2 https://doi.org/10.1063/1.555643	journal	April 1981
Thermophysical Properties of Fluid H ₂ O Kestin, J.; Sengers, J. V.; Kamgar‐Parsi, B. Journal of Physical and Chemical Reference Data, Vol. 13, Issue 1 https://doi.org/10.1063/1.555707	journal	January 1984
An internally consistent thermodynamic data set for phases of petrological interest: AN INTERNALLY CONSISTENT THERMODYNAMIC DATA SET Holland, T. J. B.; Powell, R. Journal of Metamorphic Geology, Vol. 16, Issue 3 https://doi.org/10.1111/j.1525-1314.1998.00140.x	journal	May 1998
Fluid density control on vapor-liquid partitioning of metals in hydrothermal systems Pokrovski, Gleb S.; Roux, Jacques; Harrichoury, Jean-Claude Geology, Vol. 33, Issue 8 https://doi.org/10.1130/G21475AR.1	journal	August 2005
CuCl Complexation in the Vapor Phase: Insights from Ab Initio Molecular Dynamics Simulations Mei, Yuan; Liu, Weihua; Migdiov, A. A. Geofluids, Vol. 2018 https://doi.org/10.1155/2018/4279124	journal	January 2018
Hydrated metal ions in aqueous solution: How regular are their structures? Persson, Ingmar Pure and Applied Chemistry, Vol. 82, Issue 10 https://doi.org/10.1351/PAC-CON-09-10-22	journal	August 2010
Hydrothermal Mobilisation of the Rare Earth Elements - a Tale of "Ceria" and "Yttria" Williams-Jones, A. E.; Migdisov, A. A.; Samson, I. M. Elements, Vol. 8, Issue 5 https://doi.org/10.2113/gselements.8.5.355	journal	October 2012
Theoretical prediction of the thermodynamic behavior of aqueous electrolytes by high pressures and temperatures; IV, Calculation of activity coefficients, osmotic coefficients, and apparent molal and standard and relative partial molal properties to 600 degrees C and 5kb Helgeson, H. C.; Kirkham, D. H.; Flowers, G. C. American Journal of Science, Vol. 281, Issue 10 https://doi.org/10.2475/ajs.281.10.1249	journal	December 1981

Similar Records

Quantification of the REE³⁺ aqua ions and chloride species in aqueous fluids by in situ Raman spectroscopy using perturbations of the water band

Journal Article · Thu Feb 13 00:00:00 UTC 2025 · Chemical Geology · OSTI ID:2522062

Maciag, Bryan J.; Gysi, Alexander P.; Hurtig, Nicole C.

Hydrothermal solution calorimetry in acidic aqueous solutions and revisiting the standard partial molal thermodynamic properties of Nd³⁺ from 25 to 300 °C

Journal Article · Thu Sep 05 00:00:00 UTC 2024 · Geochimica et Cosmochimica Acta · OSTI ID:2522073

Penarrieta, Yerko Figueroa; Gysi, Alexander P.

Electrochemistry and redox chemistry of H sub 2 OFe sup III SiW sub 11 O sub 39 sup 5 minus in the presence of H sub 2 O sub 2 and OH

Journal Article · Wed May 16 04:00:00 UTC 1990 · Inorganic Chemistry; (USA) · OSTI ID:6669096

Toth, J E; Anson, F C; Melton, J D; +2 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Title: An Experimental Study of the Solubility of Rare Earth Chloride Salts (La, Nd, Er) in HCl Bearing Water Vapor from 350 – 425 °C

Citation Formats

References (45)

Similar Records

Related Subjects