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Title: Pushing the limits of the electrochemical window with pulse radiolysis in chloroform

Abstract

Pulse radiolysis (PR) enables the full redox window of a solvent to be accessed, as it does not require electrodes or electrolyte which limit the potentials accessible in voltammetry measurements. PR in chloroform has the additional possibility to enable reaching highly positive potentials because of its large ionization potential (IP). We report PR experiments demonstrated the formation of the (deuterated) chloroform radical cation CDCl3+˙, identifying it as the source of the broad absorption in the visible part of the spectrum. Results indicated that solutes with a redox potential up to +3.7 V vs. Fc/Fc+ can be oxidized by CDCl3+˙, which is far beyond what is possible with electrochemical techniques. Oxidation is not efficient because of rapid geminate recombination with chloride counterions, but also due to rapid decomposition of CDCl3+˙ which limits the yield of otherwise longer-lived free ions. The rapid, 6 ± 3 ns, decomposition, confirmed by two independent experiments, means that a solute must be present at a concentration >100 mM to capture >90% of the free holes formed. Addition of ethene removes the broad, overlapping absorptions from ubiquitous (chlorine atom, solute) complexes created by PR in halogenated solvents enabling clear observation of solute cations. The results also unravelmore » the complex radiation chemistry of chloroform including the large reported value G(–CHCl3) = 12 molecules/100 eV for the decomposition of chloroform molecules.« less

Authors:
ORCiD logo [1]; ORCiD logo [1];  [2];  [3]; ORCiD logo [1]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States)
  2. Stephen F. Austin State Univ., Nacogdoches, TX (United States)
  3. Kyoto Inst. of Technology (Japan)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1646574
Alternate Identifier(s):
OSTI ID: 1634252
Report Number(s):
BNL-216223-2020-JAAM
Journal ID: ISSN 1463-9076
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP
Additional Journal Information:
Journal Volume: 22; Journal Issue: 26; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY

Citation Formats

Bird, Matthew J., Cook, Andrew R., Zamadar, Matibur, Asaoka, Sadayuki, and Miller, John R.. Pushing the limits of the electrochemical window with pulse radiolysis in chloroform. United States: N. p., 2020. Web. https://doi.org/10.1039/d0cp01948h.
Bird, Matthew J., Cook, Andrew R., Zamadar, Matibur, Asaoka, Sadayuki, & Miller, John R.. Pushing the limits of the electrochemical window with pulse radiolysis in chloroform. United States. https://doi.org/10.1039/d0cp01948h
Bird, Matthew J., Cook, Andrew R., Zamadar, Matibur, Asaoka, Sadayuki, and Miller, John R.. Fri . "Pushing the limits of the electrochemical window with pulse radiolysis in chloroform". United States. https://doi.org/10.1039/d0cp01948h. https://www.osti.gov/servlets/purl/1646574.
@article{osti_1646574,
title = {Pushing the limits of the electrochemical window with pulse radiolysis in chloroform},
author = {Bird, Matthew J. and Cook, Andrew R. and Zamadar, Matibur and Asaoka, Sadayuki and Miller, John R.},
abstractNote = {Pulse radiolysis (PR) enables the full redox window of a solvent to be accessed, as it does not require electrodes or electrolyte which limit the potentials accessible in voltammetry measurements. PR in chloroform has the additional possibility to enable reaching highly positive potentials because of its large ionization potential (IP). We report PR experiments demonstrated the formation of the (deuterated) chloroform radical cation CDCl3+˙, identifying it as the source of the broad absorption in the visible part of the spectrum. Results indicated that solutes with a redox potential up to +3.7 V vs. Fc/Fc+ can be oxidized by CDCl3+˙, which is far beyond what is possible with electrochemical techniques. Oxidation is not efficient because of rapid geminate recombination with chloride counterions, but also due to rapid decomposition of CDCl3+˙ which limits the yield of otherwise longer-lived free ions. The rapid, 6 ± 3 ns, decomposition, confirmed by two independent experiments, means that a solute must be present at a concentration >100 mM to capture >90% of the free holes formed. Addition of ethene removes the broad, overlapping absorptions from ubiquitous (chlorine atom, solute) complexes created by PR in halogenated solvents enabling clear observation of solute cations. The results also unravel the complex radiation chemistry of chloroform including the large reported value G(–CHCl3) = 12 molecules/100 eV for the decomposition of chloroform molecules.},
doi = {10.1039/d0cp01948h},
journal = {Physical Chemistry Chemical Physics. PCCP},
number = 26,
volume = 22,
place = {United States},
year = {2020},
month = {6}
}

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