Local molecular environment drives speciation and reactivity of ion complexes in concentrated salt solution

Rampal, Nikhil; Wang, Hsiu-Wen; Biriukov, Denys; Brady, Alexander B.; Neuefeind, Joerg C.; Předota, Milan; Stack, Andrew G.

doi:10.1016/j.molliq.2021.116898

Title: Local molecular environment drives speciation and reactivity of ion complexes in concentrated salt solution

Journal Article · 16 September 2021 · Journal of Molecular Liquids

DOI: https://doi.org/10.1016/j.molliq.2021.116898 · OSTI ID:1840173

^[1];

^[2]; Biriukov, Denys ^[3]; Brady, Alexander B. ^[2];

^[2]; Předota, Milan ^[4];

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Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Columbia Univ., New York, NY (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Univ. of South Bohemia, České Budějovice (Czech Republic); Czech Academy of Sciences, Prague (Czech Republic). Inst. of Organic Chemistry and Biochemistry
Univ. of South Bohemia, České Budějovice (Czech Republic)

The speciation and reactivity of aqueous salt solutions are important for a wide variety of applications. However, application of this information is inhibited by broad disagreement about composition, mechanisms, and structure in concentrated solutions especially. Here, neutron diffraction with isotopic substitution measurements on aqueous zinc chloride solutions are used to calibrate molecular dynamics simulations that include effective electronic polarization. This allows us to probe the origin of speciation and reactivity of zinc chloride-water ion complexes, ZnCl_x(H₂O)_y^2-x (x ≤ 4 and y ≤ 6), by comparing the reactivity of species in concentrated (4.5 m) and dilute (0.01 m) conditions. Within the concentrated solution, it is found that the extended solvation environment is dominated by solvent-separated ion complexes whose presence increases the free energy of activation for interconversion of species while simultaneously enhancing their thermodynamic stability. This concentration-dependent reactivity and stability suggests that other reactions, such as the nucleation of solid phases, will also be affected.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1840173

Journal Information:: Journal of Molecular Liquids, Journal Name: Journal of Molecular Liquids Journal Issue: 10 Vol. 340; ISSN 0167-7322

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (67)

GROMACS: Fast, flexible, and free Van Der Spoel, David; Lindahl, Erik; Hess, Berk Journal of Computational Chemistry, Vol. 26, Issue 16 https://doi.org/10.1002/jcc.20291	journal	January 2005
PACKMOL: A package for building initial configurations for molecular dynamics simulations Martínez, L.; Andrade, R.; Birgin, E. G. Journal of Computational Chemistry, Vol. 30, Issue 13 https://doi.org/10.1002/jcc.21224	journal	October 2009
Metadynamics: Metadynamics Barducci, Alessandro; Bonomi, Massimiliano; Parrinello, Michele Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 1, Issue 5 https://doi.org/10.1002/wcms.31	journal	February 2011
Fast Parallel Algorithms for Short-Range Molecular Dynamics Plimpton, Steve Journal of Computational Physics, Vol. 117, Issue 1 https://doi.org/10.1006/jcph.1995.1039	journal	March 1995
The solubility of barite and celestite in sodium sulfate: Evaluation of thermodynamic data Felmy, A. R.; Rai, Dhanpat; Amonette, J. E. Journal of Solution Chemistry, Vol. 19, Issue 2 https://doi.org/10.1007/BF00646611	journal	February 1990
Activity coefficient measurements of the system HCl?ZnCl2?H2O at 25 and 35�C Tialowska-Mocharla, Hanna; Manohar, S.; Atkinson, Gordon Journal of Solution Chemistry, Vol. 21, Issue 6 https://doi.org/10.1007/BF00649563	journal	June 1992
GROMACS: A message-passing parallel molecular dynamics implementation Berendsen, H. J. C.; van der Spoel, D.; van Drunen, R. Computer Physics Communications, Vol. 91, Issue 1-3 https://doi.org/10.1016/0010-4655(95)00042-E	journal	September 1995
The solubilities of calcite, aragonite and vaterite in CO2-H2O solutions between 0 and 90°C, and an evaluation of the aqueous model for the system CaCO3-CO2-H2O Plummer, L. Niel; Busenberg, Eurybiades Geochimica et Cosmochimica Acta, Vol. 46, Issue 6 https://doi.org/10.1016/0016-7037(82)90056-4	journal	June 1982
The incorporation of Mg2+ and Sr2+ into calcite overgrowths: influences of growth rate and solution composition Mucci, Alfonso; Morse, John W. Geochimica et Cosmochimica Acta, Vol. 47, Issue 2 https://doi.org/10.1016/0016-7037(83)90135-7	journal	February 1983
Calculation of the thermodynamic and transport properties of aqueous species at high pressures and temperatures: Standard partial molal properties of inorganic neutral species Shock, Everett L.; Helgeson, Harold C.; Sverjensky, Dimitri A. Geochimica et Cosmochimica Acta, Vol. 53, Issue 9 https://doi.org/10.1016/0016-7037(89)90341-4	journal	September 1989
Extraction of zinc chloride from aqueous chloride solutions by hydrocarbon solutions of quaternary ammonium chloride salt Attempt to evaluate the zinc chloride complexes by means of the extraction data Scibona, G.; Orlandini, F.; Danesi, P. R. Journal of Inorganic and Nuclear Chemistry, Vol. 28, Issue 5 https://doi.org/10.1016/0022-1902(66)80459-1	journal	May 1966
Computational limits of classical molecular dynamics simulations Plimpton, Steve Computational Materials Science, Vol. 4, Issue 4 https://doi.org/10.1016/0927-0256(95)00037-1	journal	November 1995
Water structure around chloride ions in the presence of biological macromolecules Wilson, J. E.; Ansell, S.; Enderby, J. E. Chemical Physics Letters, Vol. 278, Issue 1-3 https://doi.org/10.1016/S0009-2614(97)01018-X	journal	October 1997
Water exchange on metal ions: experiments and simulations Helm, L.; Merbach, A. E. Coordination Chemistry Reviews, Vol. 187, Issue 1 https://doi.org/10.1016/S0010-8545(99)90232-1	journal	June 1999
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
PLUMED 2: New feathers for an old bird Tribello, Gareth A.; Bonomi, Massimiliano; Branduardi, Davide Computer Physics Communications, Vol. 185, Issue 2 https://doi.org/10.1016/j.cpc.2013.09.018	journal	February 2014
Metadyn View: Fast web-based viewer of free energy surfaces calculated by metadynamics Hošek, Petr; Spiwok, Vojtěch Computer Physics Communications, Vol. 198 https://doi.org/10.1016/j.cpc.2015.08.037	journal	January 2016
Zinc complexation in chloride-rich hydrothermal fluids (25–600 °C): A thermodynamic model derived from ab initio molecular dynamics Mei, Yuan; Sherman, David M.; Liu, Weihua Geochimica et Cosmochimica Acta, Vol. 150 https://doi.org/10.1016/j.gca.2014.09.023	journal	February 2015
Prenucleation clusters and non-classical nucleation Gebauer, Denis; Cölfen, Helmut Nano Today, Vol. 6, Issue 6 https://doi.org/10.1016/j.nantod.2011.10.005	journal	December 2011
The Nanoscale Ordered MAterials Diffractometer NOMAD at the Spallation Neutron Source SNS Neuefeind, Jörg; Feygenson, Mikhail; Carruth, John Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 287 https://doi.org/10.1016/j.nimb.2012.05.037	journal	September 2012
Role of CaCO ₃ ° Neutral Pair in Calcium Carbonate Crystallization Genovese, Damiano; Montalti, Marco; Otálora, Fermín Crystal Growth & Design, Vol. 16, Issue 8 https://doi.org/10.1021/acs.cgd.6b00276	journal	July 2016
Thermodynamic-Kinetic Precipitation Modeling. A Case Study: The Amorphous Calcium Carbonate (ACC) Precipitation Pathway Unravelled Carino, Agnese; Testino, Andrea; Andalibi, Mohammad Reza Crystal Growth & Design, Vol. 17, Issue 4 https://doi.org/10.1021/acs.cgd.7b00006	journal	March 2017
Crystal Nucleation in Liquids: Open Questions and Future Challenges in Molecular Dynamics Simulations Sosso, Gabriele C.; Chen, Ji; Cox, Stephen J. Chemical Reviews, Vol. 116, Issue 12 https://doi.org/10.1021/acs.chemrev.5b00744	journal	May 2016
Marcus Theory of Ion-Pairing Roy, Santanu; Baer, Marcel D.; Mundy, Christopher J. Journal of Chemical Theory and Computation, Vol. 13, Issue 8 https://doi.org/10.1021/acs.jctc.7b00332	journal	July 2017
Hydration and Ion Pairing in Aqueous Mg ²⁺ and Zn ²⁺ Solutions: Force-Field Description Aided by Neutron Scattering Experiments and Ab Initio Molecular Dynamics Simulations Duboué-Dijon, Elise; Mason, Philip E.; Fischer, Henry E. The Journal of Physical Chemistry B, Vol. 122, Issue 13 https://doi.org/10.1021/acs.jpcb.7b09612	journal	October 2017
Frustration vs Prenucleation: Understanding the Surprising Stability of Supersaturated Sodium Thiosulfate Solutions Reichenbach, Judith; Wynne, Klaas The Journal of Physical Chemistry B, Vol. 122, Issue 30 https://doi.org/10.1021/acs.jpcb.8b04112	journal	July 2018
Decoding Oxyanion Aqueous Solvation Structure: A Potassium Nitrate Example at Saturation Wang, Hsiu-Wen; Vlcek, Lukas; Neuefeind, Joerg C. The Journal of Physical Chemistry B, Vol. 122, Issue 30 https://doi.org/10.1021/acs.jpcb.8b05895	journal	July 2018
Thermodynamically Consistent Force Field for Molecular Dynamics Simulations of Alkaline-Earth Carbonates and Their Aqueous Speciation Raiteri, Paolo; Demichelis, Raffaella; Gale, Julian D. The Journal of Physical Chemistry C, Vol. 119, Issue 43 https://doi.org/10.1021/acs.jpcc.5b07532	journal	October 2015
Free-Energy Landscape of the Dissolution of Gibbsite at High pH Shen, Zhizhang; Kerisit, Sebastien N.; Stack, Andrew G. The Journal of Physical Chemistry Letters, Vol. 9, Issue 7 https://doi.org/10.1021/acs.jpclett.8b00484	journal	March 2018
Countercations Control Local Specific Bonding Interactions and Nucleation Mechanisms in Concentrated Water-in-Salt Solutions Wang, Hsiu-Wen; Graham, Trent R.; Mamontov, Eugene The Journal of Physical Chemistry Letters, Vol. 10, Issue 12 https://doi.org/10.1021/acs.jpclett.9b01416	journal	May 2019
Ligand Substitution Reactions at Inorganic Centers ^† Richens, David T. Chemical Reviews, Vol. 105, Issue 6 https://doi.org/10.1021/cr030705u	journal	June 2005
Dynamical aspects of the sodium(1+)-chloride ion pair association in water Rey, R.; Guardia, E. The Journal of Physical Chemistry, Vol. 96, Issue 11 https://doi.org/10.1021/j100190a104	journal	May 1992
Ion-water interaction potentials derived from free energy perturbation simulations Ȧqvist, Johan The Journal of Physical Chemistry, Vol. 94, Issue 21 https://doi.org/10.1021/j100384a009	journal	October 1990
Molecular Dynamics Calculation of the Activation Volume for Water Exchange on Li ⁺ Rustad, James R.; Stack, Andrew G. Journal of the American Chemical Society, Vol. 128, Issue 46 https://doi.org/10.1021/ja066022o	journal	November 2006
Influence of Countercation Hydration Enthalpies on the Formation of Molecular Complexes: A Thorium–Nitrate Example Jin, Geng Bang; Lin, Jian; Estes, Shanna L. Journal of the American Chemical Society, Vol. 139, Issue 49 https://doi.org/10.1021/jacs.7b09363	journal	November 2017
Designing Solid Materials from Their Solute State: A Shift in Paradigms toward a Holistic Approach in Functional Materials Chemistry Gebauer, Denis; Wolf, Stephan E. Journal of the American Chemical Society, Vol. 141, Issue 11 https://doi.org/10.1021/jacs.8b13231	journal	February 2019
Modeling Water Exchange on an Aluminum Polyoxocation Stack, Andrew G.; Rustad, James R.; Casey, William H. The Journal of Physical Chemistry B, Vol. 109, Issue 50 https://doi.org/10.1021/jp0530505	journal	December 2005
Relationship between the Phase Diagram, the Glass-Forming Ability, and the Fragility of a Water/Salt Mixture Kobayashi, Mika; Tanaka, Hajime The Journal of Physical Chemistry B, Vol. 115, Issue 48 https://doi.org/10.1021/jp203855c	journal	December 2011
A Molecular Dynamics Study of Alkaline Earth Metal−Chloride Complexation in Aqueous Solution Larentzos, James P.; Criscenti, Louise J. The Journal of Physical Chemistry B, Vol. 112, Issue 45 https://doi.org/10.1021/jp802771w	journal	November 2008
Effects of Polarizability on the Hydration of the Chloride Ion Stuart, Steven J.; Berne, B. J. The Journal of Physical Chemistry, Vol. 100, Issue 29 https://doi.org/10.1021/jp961076d	journal	January 1996
Stable prenucleation mineral clusters are liquid-like ionic polymers Demichelis, Raffaella; Raiteri, Paolo; Gale, Julian D. Nature Communications, Vol. 2, Issue 1 https://doi.org/10.1038/ncomms1604	journal	September 2011
Metastable structures and isotope exchange reactions in polyoxometalate ions provide a molecular view of oxide dissolution Rustad, James R.; Casey, William H. Nature Materials, Vol. 11, Issue 3 https://doi.org/10.1038/nmat3203	journal	January 2012
Solvents can control solute molecular identity Widmer, Devon. R.; Schwartz, Benjamin J. Nature Chemistry, Vol. 10, Issue 9 https://doi.org/10.1038/s41557-018-0066-z	journal	May 2018
Resolving local configurational contributions to X-ray and neutron radial distribution functions within solutions of concentrated electrolytes – a case study of concentrated NaOH Semrouni, David; Wang, Hsiu-Wen; Clark, Sue B. Physical Chemistry Chemical Physics, Vol. 21, Issue 13 https://doi.org/10.1039/C8CP06802J	journal	January 2019
Accounting for electronic polarization in non-polarizable force fields Leontyev, Igor; Stuchebrukhov, Alexei Physical Chemistry Chemical Physics, Vol. 13, Issue 7 https://doi.org/10.1039/c0cp01971b	journal	January 2011
The hydration structure around chloride ions in aqueous solution Powell, D. Hugh; Barnes, Adrian C.; Enderby, John E. Faraday Discussions of the Chemical Society, Vol. 85 https://doi.org/10.1039/dc9888500137	journal	January 1988
Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points Henkelman, Graeme; Jónsson, Hannes The Journal of Chemical Physics, Vol. 113, Issue 22 https://doi.org/10.1063/1.1323224	journal	December 2000
The effect of water models on the interaction of the sodium–chloride ion pair in water: Molecular dynamics simulations Dang, Liem X.; Rice, Julia E.; Kollman, Peter A. The Journal of Chemical Physics, Vol. 93, Issue 10 https://doi.org/10.1063/1.459714	journal	November 1990
A classical view on nonclassical nucleation Smeets, Paul J. M.; Finney, Aaron R.; Habraken, Wouter J. E. M. Proceedings of the National Academy of Sciences, Vol. 114, Issue 38 https://doi.org/10.1073/pnas.1700342114	journal	September 2017
Escaping free-energy minima Laio, A.; Parrinello, M. Proceedings of the National Academy of Sciences, Vol. 99, Issue 20 https://doi.org/10.1073/pnas.202427399	journal	September 2002
Zn ²⁺ hydration and complexation in aqueous electrolyte solutions Powell, D. H.; Gullidge, P. M. N.; Neilson, G. W. Molecular Physics, Vol. 71, Issue 5 https://doi.org/10.1080/00268979000102351	journal	December 1990
Hoover NPT dynamics for systems varying in shape and size Melchionna, Simone; Ciccotti, Giovanni; Lee Holian, Brad Molecular Physics, Vol. 78, Issue 3 https://doi.org/10.1080/00268979300100371	journal	February 1993
Ion hydration in aqueous CaCl ₂ solutions Cummings, S.; Enderby, J. E.; Howe, R. A. Journal of Physics C: Solid State Physics, Vol. 13, Issue 1 https://doi.org/10.1088/0022-3719/13/1/005	journal	January 1980
The structure of Cu ²⁺ aqueous solutions Salmon, P. S.; Neilson, G. W.; Enderby, J. E. Journal of Physics C: Solid State Physics, Vol. 21, Issue 8 https://doi.org/10.1088/0022-3719/21/8/010	journal	March 1988
Structure of liquid and glassy ZnCl 2 Zeidler, Anita; Salmon, Philip S.; Martin, Richard A. Physical Review B, Vol. 82, Issue 10 https://doi.org/10.1103/PhysRevB.82.104208	journal	September 2010
Possible Link of the V -Shaped Phase Diagram to the Glass-Forming Ability and Fragility in a Water-Salt Mixture Kobayashi, Mika; Tanaka, Hajime Physical Review Letters, Vol. 106, Issue 12 https://doi.org/10.1103/PhysRevLett.106.125703	journal	March 2011
Die Kristallstruktur des ZnCl ₂ .4/3H ₂ O Follner, H.; Brehler, B. Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 26, Issue 11 https://doi.org/10.1107/S0567740870004715	journal	November 1970
Supersaturated calcium carbonate solutions are classical Henzler, Katja; Fetisov, Evgenii O.; Galib, Mirza Science Advances, Vol. 4, Issue 1 https://doi.org/10.1126/sciadv.aao6283	journal	January 2018
Kinetic Evidence for Five-Coordination in AlOH(aq)2+ Ion Swaddle, T. W. Science, Vol. 308, Issue 5727 https://doi.org/10.1126/science.1110231	journal	June 2005
Stable Prenucleation Calcium Carbonate Clusters Gebauer, Denis; Völkel, Antje; Cölfen, Helmut Science, Vol. 322, Issue 5909 https://doi.org/10.1126/science.1164271	journal	December 2008
Microscopic Evidence for Liquid-Liquid Separation in Supersaturated CaCO3 Solutions Wallace, A. F.; Hedges, L. O.; Fernandez-Martinez, A. Science, Vol. 341, Issue 6148 https://doi.org/10.1126/science.1230915	journal	August 2013
Nucleation from Solution Myerson, A. S.; Trout, B. L. Science, Vol. 341, Issue 6148 https://doi.org/10.1126/science.1243022	journal	August 2013
The Structure of Zinc Chloride Complexes in Aqueous Solution Maeda, M.; Ito, T.; Hori, M. Zeitschrift für Naturforschung A, Vol. 51, Issue 1-2 https://doi.org/10.1515/zna-1996-1-210	journal	February 1996
The Solubility of Am0HC03(c) and the Aqueous Thermodynamics of the System Na+-Am3+-HC03–-C032-0H--H20 Felmy, Andrew R.; Rai, Dhanpat; Fulton, Robert W. Radiochimica Acta, Vol. 50, Issue 4 https://doi.org/10.1524/ract.1990.50.4.193	journal	January 1990
On classical and non-classical views on nucleation Gebauer, Denis; Raiteri, Paolo; Gale, Julian D. American Journal of Science, Vol. 318, Issue 9 https://doi.org/10.2475/09.2018.05	journal	November 2018
Thermodynamics of hydrothermal systems at elevated temperatures and pressures Helgeson, H. C. American Journal of Science, Vol. 267, Issue 7 https://doi.org/10.2475/ajs.267.7.729	journal	September 1969
Formation of Corrosion Products on Open and Confined Zinc Surfaces Exposed to Periodic Wet/Dry Conditions Zhu, F.; Persson, D.; Thierry, D. CORROSION, Vol. 56, Issue 12 https://doi.org/10.5006/1.3280514	journal	December 2000

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