Direct Observation of Ion Pairing in Aqueous Nitric Acid Using 2D Infrared Spectroscopy

Lewis, Nicholas H.  C.; Fournier, Joseph A.; Carpenter, William B.; Tokmakoff, Andrei

doi:10.1021/acs.jpcb.8b10019

Title: Direct Observation of Ion Pairing in Aqueous Nitric Acid Using 2D Infrared Spectroscopy

Journal Article · 06 December 2018 · Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry

DOI: https://doi.org/10.1021/acs.jpcb.8b10019 · OSTI ID:1600136

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Univ. of Chicago, IL (United States); The University of Chicago
Washington Univ., St. Louis, MO (United States)
Univ. of Chicago, IL (United States)

Ion–ion interactions and ion pairing play an important role in the properties of concentrated electrolyte solutions, yet remain difficult to study due to the heterogeneous and highly dynamic behavior of these systems. In concentrated acid solutions, these questions take on a further level of complexity because the structure of the aqueous proton itself is uncertain and may be influenced by the counterion. Here, we address these questions by studying the IR spectra of nitric acid as a function of concentration in H2O and comparing these to the spectra of several alkali nitrate salts. We show how the close proximity between cations and NO3– ions in solution at high concentration affect the IR spectra and therefore the molecular structures. Using two-dimensional IR spectroscopy, we demonstrate the formation of contracted ion pair configurations in nitric acid solutions between NO3– ions and H+(aq) via the observation of a distinct anisotropic intermolecular crosspeak between these species. By studying the concentration dependence of this spectral feature, we show that this ion-paired configuration exists in solution at concentrations as low as 2 M and suggests that the structure of H+(aq) solvation complex in these ion pairs differs from the structure in bulk solution.

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Research Organization:: Univ. of Chicago, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0014305

OSTI ID:: 1600136

Journal Information:: Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry, Journal Name: Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry Journal Issue: 1 Vol. 123; ISSN 1520-6106

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited By (2)

Hydration of ferric chloride and nitrate in aqueous solutions: water-mediated ion pairing revealed by Raman spectroscopy Baumler, Stephen M.; Hartt V., William H.; Allen, Heather C. Physical Chemistry Chemical Physics, Vol. 21, Issue 35 https://doi.org/10.1039/c9cp01392j	journal	January 2019
Entropic barriers in the kinetics of aqueous proton transfer Carpenter, William B.; Lewis, Nicholas H. C.; Fournier, Joseph A. The Journal of Chemical Physics, Vol. 151, Issue 3 https://doi.org/10.1063/1.5108907	journal	July 2019

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