Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

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]
+ Show Author Affiliations
  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. doi:10.1039/d0cp01948h.
Copy to clipboard
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
Copy to clipboard
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.
Copy to clipboard
@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}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1039/d0cp01948h
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

A Practical Beginner’s Guide to Cyclic Voltammetry
journal, November 2017

  • Elgrishi, Noémie; Rountree, Kelley J.; McCarthy, Brian D.
  • Journal of Chemical Education, Vol. 95, Issue 2
  • DOI: 10.1021/acs.jchemed.7b00361

Pulse‐Radiolysis Observation of Molecular Cations of Aromatic Compounds in Halogenated Liquids
journal, February 1969

  • Arai, Shigeyoshi; Ueda, Hisashi; Firestone, Richard F.
  • The Journal of Chemical Physics, Vol. 50, Issue 3
  • DOI: 10.1063/1.1671159

Pulse radiolysis studies on charge carriers in conjugated polymers
journal, February 2000

  • Burrows, H. D.; Miguel, M. da G.; Monkman, A. P.
  • The Journal of Chemical Physics, Vol. 112, Issue 6
  • DOI: 10.1063/1.480883

Hole formation and transfer in poly[9,9-di(ethylhexyl)fluorene] and an amine end-capped derivative in solution
journal, February 2004

Rapid “Step Capture” of Holes in Chloroform during Pulse Radiolysis
journal, July 2013

  • Cook, Andrew R.; Bird, Matthew J.; Asaoka, Sadayuki
  • The Journal of Physical Chemistry A, Vol. 117, Issue 33
  • DOI: 10.1021/jp405349u

Solute radical cation yields in the pulse radiolysis of solutions of aromatic amines in chlorinated hydrocarbons
journal, January 1972

  • Burrows, H. D.; Greatorex, D.; Kemp, T. J.
  • The Journal of Physical Chemistry, Vol. 76, Issue 1
  • DOI: 10.1021/j100645a004

Chloroform Anion Fragmentation in Liquid Methylcyclohexane:  t -0.6 Simulation of the Geminate Ion Kinetics
journal, July 1999

  • Bühler, Rolf E.; Domazou, Anastasia S.; Katsumura, Yosuke
  • The Journal of Physical Chemistry A, Vol. 103, Issue 26
  • DOI: 10.1021/jp984760w

Unexpectedly Large Spin Coherence Effects in the Recombination Fluorescence from Irradiated Highly Polar Solutions on a Nanosecond Time Scale
journal, September 2017

Geminate Ion Kinetics for Hexa-, Penta- and Tetrachloroethane in Liquid Methylcyclohexane (MCH):  Effect of the Anion Lifetimes
journal, December 2003

  • Quadir, M. A.; Azuma, T.; Domazou, A. S.
  • The Journal of Physical Chemistry A, Vol. 107, Issue 51
  • DOI: 10.1021/jp030481j

Resonant dissociative electron transfer of the presolvated electron to CCl4 in liquid: Direct observation and lifetime of the CCl4*− transition state
journal, January 2008

  • Wang, C. -R.; Drew, K.; Luo, T.
  • The Journal of Chemical Physics, Vol. 128, Issue 4
  • DOI: 10.1063/1.2836749

Geminate Charge Recombination in Liquid Alkane with Concentrated CCl 4 : Effects of CCl 4 Radical Anion and Narrowing of Initial Distribution of Cl –
journal, September 2011

  • Saeki, Akinori; Yamamoto, Naoto; Yoshida, Yoichi
  • The Journal of Physical Chemistry A, Vol. 115, Issue 36
  • DOI: 10.1021/jp205989r

Kinetics of the γ-Ray-Induced Decomposition of Chloroform 1
journal, March 1965

  • Werner, Horst R.; Firestone, Richard F.
  • The Journal of Physical Chemistry, Vol. 69, Issue 3
  • DOI: 10.1021/j100887a023

Positive Ion Scavenging in the Radiolysis of Liquid Chloroform
journal, November 1970

  • Baxter, J. N.; Bibler, N. E.
  • The Journal of Chemical Physics, Vol. 53, Issue 9
  • DOI: 10.1063/1.1674515

Dose rate effects in the steady and pulse radiolysis of liquid chloroform
journal, August 1971

Combined Effects of Dose Rate and Temperature in the Radiolysis of Liquid Chloroform. Application of Homogeneous Kinetics to the Radiolytic System 1
journal, November 1966

  • Abramson, Fred P.; Firestone, Richard F.
  • The Journal of Physical Chemistry, Vol. 70, Issue 11
  • DOI: 10.1021/j100883a040

Effects of Temperature and Added Hexachloroethane on the Radiolyses of Carbon Tetrachloride and Chloroform
journal, May 1961

  • Johnston, F. J.; Chen, Tung-Ho; Wong, K. Y.
  • The Journal of Physical Chemistry, Vol. 65, Issue 5
  • DOI: 10.1021/j100823a006

Radiolysis of Chloroform and Carbon Tetrachloride
journal, August 1960

  • Chen, T. H.; Wong, K. Y.; Johnston, F. J.
  • The Journal of Physical Chemistry, Vol. 64, Issue 8
  • DOI: 10.1021/j100837a013

Die Zersetzung des Chloroforms durch Gamma-Strahlen und durch Ultraschallwellen
journal, October 1958

The Radiation Chemistry of Chloroform
journal, March 1961

  • Ottolenghi, Michael; Stein, Gabriel
  • Radiation Research, Vol. 14, Issue 3
  • DOI: 10.2307/3570922

Radiolysis of Chloroform in the Intense Radiation Pulse from a Nuclear Explosion
journal, July 1968

  • Bibler, N. E.; Hyder, M. L.
  • Nature, Vol. 219, Issue 5152
  • DOI: 10.1038/219374a0

Direct measurement of the absolute kinetics of chlorine atom in carbon tetrachloride
journal, January 1990

  • Chateauneuf, John E.
  • Journal of the American Chemical Society, Vol. 112, Issue 1
  • DOI: 10.1021/ja00157a066

Charge-transfer absorption spectra of chlorine atoms in halogenated solvents
journal, December 1989

Photoisomerization and Photoinduced Reactions in Liquid CCl 4 and CHCl 3
journal, September 2013

  • Abou-Chahine, Fawzi; Preston, Thomas J.; Dunning, Greg T.
  • The Journal of Physical Chemistry A, Vol. 117, Issue 50
  • DOI: 10.1021/jp406687x

Picosecond 266 nm multiphoton laser photolysis of liquid alkyl chlorides: Production of ionic species
journal, August 1985

The Laser Two-photon Photolysis of Liquid Carbon Tetrachloride†
journal, January 2006

Spectroscopic detection and reactivity of the chlorine atom-carbon disulfide molecular complex
journal, March 1993

  • Chateauneuf, John E.
  • Journal of the American Chemical Society, Vol. 115, Issue 5
  • DOI: 10.1021/ja00058a042

Solvent Effects in the Reactions of Free Radicals and Atoms. VIII. The Photochlorination of Aralkyl Hydrocarbons
journal, October 1963

  • Russell, Glen A.; Ito, Akihiko.; Hendry, Dale G.
  • Journal of the American Chemical Society, Vol. 85, Issue 19
  • DOI: 10.1021/ja00902a022

The LEAF picosecond pulse radiolysis facility at Brookhaven National Laboratory
journal, November 2004

  • Wishart, James F.; Cook, Andrew R.; Miller, John R.
  • Review of Scientific Instruments, Vol. 75, Issue 11
  • DOI: 10.1063/1.1807004

Reaction of CS2/Cl complexes with alcohols studied by pulse radiolysis
journal, December 2005

Aqueous Solvation Free Energies of Ions and Ion−Water Clusters Based on an Accurate Value for the Absolute Aqueous Solvation Free Energy of the Proton
journal, August 2006

  • Kelly, Casey P.; Cramer, Christopher J.; Truhlar, Donald G.
  • The Journal of Physical Chemistry B, Vol. 110, Issue 32
  • DOI: 10.1021/jp063552y

Single-Ion Solvation Free Energies and the Normal Hydrogen Electrode Potential in Methanol, Acetonitrile, and Dimethyl Sulfoxide
journal, January 2007

  • Kelly, Casey P.; Cramer, Christopher J.; Truhlar, Donald G.
  • The Journal of Physical Chemistry B, Vol. 111, Issue 2
  • DOI: 10.1021/jp065403l

Driving Force Dependence of Intermolecular Electron-Transfer Reactions of Fullerenes
journal, April 2003

  • Fukuzumi, Shunichi; Ohkubo, Kei; Imahori, Hiroshi
  • Chemistry - A European Journal, Vol. 9, Issue 7
  • DOI: 10.1002/chem.200390182

Efficiencies of photoinduced electron-transfer reactions: role of the Marcus inverted region in return electron transfer within geminate radical-ion pairs
journal, May 1990

  • Gould, Ian R.; Ege, Deniz; Moser, Jacques E.
  • Journal of the American Chemical Society, Vol. 112, Issue 11
  • DOI: 10.1021/ja00167a027

Dissociation energies of the benzene dimer and dimer cation
journal, June 1987

  • Grover, J. R.; Walters, E. A.; Hui, E. T.
  • The Journal of Physical Chemistry, Vol. 91, Issue 12
  • DOI: 10.1021/j100296a026

Mobilities of Radical Cations and Anions, Dimer Radical Anions, and Relative Electron Affinities by Times of Flight in n-Hexane
journal, September 1994

  • Lim, S. K.; Burba, M. E.; Albrecht, A. C.
  • The Journal of Physical Chemistry, Vol. 98, Issue 38
  • DOI: 10.1021/j100089a048
    Sort by:
    [ × clear filter / sort ]

    Similar Records in DOE PAGES and OSTI.GOV collections: