Preferential Solvation of an Asymmetric Redox Molecule

Journal Article · Thu Dec 15 04:00:00 EST 2016 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.6b09114· OSTI ID:1340794

Han, Kee Sung; Rajput, Nav Nidhi; Vijayakumar, M.; Wei, Xiaoliang; Wang, Wei; Hu, Jianzhi; Persson, Kristin A.; Mueller, Karl T.

The fundamental correlations between inter-molecular interactions, solvation structure and functionality of electrolytes are in many cases unknown, particularly for multi-component liquid systems. In this work, we explore such correlations by investigating the complex interplay between solubility and solvation structure for the electrolyte system comprising N-(ferrocenylmethyl)-N,N-dimethyl-N-ethylammonium bistrifluoromethylsulfonimide (Fc1N112-TFSI) dissolved in a ternary carbonate solvent mixture using combined NMR relaxation and computational analyses. Probing the evolution of the solvent-solvent, ion-solvent and ion-ion interactions with an increase in solute concentration provides a molecular level understanding of the solubility limit of the Fc1N112-TFSI system. An increase in solute con-centration leads to pronounced Fc1N112-TFSI contact-ion pair formation by diminishing solvent-solvent and ion-solvent type interactions. At the solubility limit, the precipitation of solute is initiated through agglomeration of contact-ion pairs due to overlapping solvation shells.

• Research Organization: Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
• Sponsoring Organization: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
• DOE Contract Number: AC05-76RL01830
• OSTI ID: 1340794
• Report Number(s): PNNL-SA-113547; 48681; KC0208010
• Journal Information: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 49 Vol. 120; ISSN 1932-7447
• Publisher: American Chemical Society
• Country of Publication: United States
• Language: English

Related Subjects

Environmental Molecular Sciences Laboratory