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

Bird, Matthew J.; Cook, Andrew R.; Zamadar, Matibur; Asaoka, Sadayuki; Miller, John R.

doi:10.1039/d0cp01948h

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

Journal Article · 12 June 2020 · Physical Chemistry Chemical Physics. PCCP

DOI: https://doi.org/10.1039/d0cp01948h · OSTI ID:1646574

^[1];

^[1]; Zamadar, Matibur ^[2]; Asaoka, Sadayuki ^[3];

^[1]

Brookhaven National Lab. (BNL), Upton, NY (United States)
Stephen F. Austin State Univ., Nacogdoches, TX (United States)
Kyoto Inst. of Technology (Japan)

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.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

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

Grant/Contract Number:: SC0012704

OSTI ID:: 1646574

Alternate ID(s):: OSTI ID: 1634252

Report Number(s):: BNL-216223-2020-JAAM

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Vol. 22, Issue 26; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 6 works

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