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Title: Entropic barriers in the kinetics of aqueous proton transfer

Abstract

Aqueous proton transport is uniquely rapid among aqueous processes, mediated by fluctuating hydrogen bond reorganization in liquid water. In a process known as Grotthuss diffusion, the excess charge diffuses primarily by sequential proton transfers between water molecules rather than standard Brownian motion, which explains the anomalously high electrical conductivity of acidic solutions. Employing ultrafast IR spectroscopy, we use the orientational anisotropy decay of the bending vibrations of the hydrated proton complex to study herein the picosecond aqueous proton transfer kinetics as a function of temperature, concentration, and counterion. We find that the orientational anisotropy decay exhibits Arrhenius behavior, with an apparent activation energy of 2.4 kcal/mol in 1M and 2M HCl. Interestingly, acidic solutions at high concentration with longer proton transfer time scales display corresponding decreases in activation energy. We interpret this counterintuitive trend by considering the entropic and enthalpic contributions to the activation free energy for proton transfer. Halide counteranions at high concentrations impose entropic barriers to proton transfer in the form of constraints on the solution’s collective H-bond fluctuations and obstruction of potential proton transfer pathways. The corresponding proton transfer barrier decreases due to weaker water-halide H-bonds in close proximity to the excess proton, but the entropic effectsmore » dominate and« less

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
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  1. Univ. of Chicago, IL (United States)
Publication Date:
Research Org.:
Univ. of Chicago, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Arnold O. Beckman Foundation
OSTI Identifier:
1612141
Alternate Identifier(s):
OSTI ID: 1542538
Grant/Contract Number:  
SC0014305
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 151; Journal Issue: 3; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 74 ATOMIC AND MOLECULAR PHYSICS; Chemistry; Physics; Chemical bonding; Infrared spectroscopy; Activation energies; Ions and properties; Ultrafast vibrational spectroscopy; Solvation; Proton diffusion

Citation Formats

Carpenter, William B., Lewis, Nicholas H. C., Fournier, Joseph A., and Tokmakoff, Andrei. Entropic barriers in the kinetics of aqueous proton transfer. United States: N. p., 2019. Web. doi:10.1063/1.5108907.
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Carpenter, William B., Lewis, Nicholas H. C., Fournier, Joseph A., & Tokmakoff, Andrei. Entropic barriers in the kinetics of aqueous proton transfer. United States. https://doi.org/10.1063/1.5108907
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Carpenter, William B., Lewis, Nicholas H. C., Fournier, Joseph A., and Tokmakoff, Andrei. Mon . "Entropic barriers in the kinetics of aqueous proton transfer". United States. https://doi.org/10.1063/1.5108907. https://www.osti.gov/servlets/purl/1612141.
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@article{osti_1612141,
title = {Entropic barriers in the kinetics of aqueous proton transfer},
author = {Carpenter, William B. and Lewis, Nicholas H. C. and Fournier, Joseph A. and Tokmakoff, Andrei},
abstractNote = {Aqueous proton transport is uniquely rapid among aqueous processes, mediated by fluctuating hydrogen bond reorganization in liquid water. In a process known as Grotthuss diffusion, the excess charge diffuses primarily by sequential proton transfers between water molecules rather than standard Brownian motion, which explains the anomalously high electrical conductivity of acidic solutions. Employing ultrafast IR spectroscopy, we use the orientational anisotropy decay of the bending vibrations of the hydrated proton complex to study herein the picosecond aqueous proton transfer kinetics as a function of temperature, concentration, and counterion. We find that the orientational anisotropy decay exhibits Arrhenius behavior, with an apparent activation energy of 2.4 kcal/mol in 1M and 2M HCl. Interestingly, acidic solutions at high concentration with longer proton transfer time scales display corresponding decreases in activation energy. We interpret this counterintuitive trend by considering the entropic and enthalpic contributions to the activation free energy for proton transfer. Halide counteranions at high concentrations impose entropic barriers to proton transfer in the form of constraints on the solution’s collective H-bond fluctuations and obstruction of potential proton transfer pathways. The corresponding proton transfer barrier decreases due to weaker water-halide H-bonds in close proximity to the excess proton, but the entropic effects dominate and},
doi = {10.1063/1.5108907},
journal = {Journal of Chemical Physics},
number = 3,
volume = 151,
place = {United States},
year = {Mon Jul 15 00:00:00 EDT 2019},
month = {Mon Jul 15 00:00:00 EDT 2019}
}
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https://doi.org/10.1063/1.5108907
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Cited by: 12 works
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Figures / Tables:

FIG. 1 FIG. 1: FTIR spectrum of H2O (black dashed line), 2M NaCl (blue line), 2M HCl (red line), and the 2M HCl–2M NaCl difference (green line). The bending modes of hydrated proton complexes, δH+, are contained in the feature centered at 1750 cm−1.
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