One-Electron Reduction of 2-Nitrotoluene, Nitrocyclopentane, and 1-Nitrobutane in Room Temperature Ionic Liquids: A Comparative Study of Butler–Volmer and Symmetric Marcus–Hush Theories Using Microdisk Electrodes

Eden E. L. Tanner, Edward O. Barnes, Peter Goodrich, Christopher Hardacre, Richard G. Compton*

*Corresponding author for this work

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

The voltammetry for the reduction of 2-nitrotoluene at a gold microdisk electrode is reported in two ionic liquids: trihexyltetradecylphosphonium tris(pentafluoroethyl)trifluorophosphate ([P-14,P-6,P-6,P-6][FAP]) and 1-ethyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([Emim][NTf2]). The reduction of nitrocyclopentane (NCP) and 1-nitrobutane (BuN) was investigated using voltammetry at a gold microdisk electrode in the ionic liquid [P-14,P-6,P-6,P-6][FAP]. Simulated voltammograms, generated through the use of ButlerVolmer theory and symmetric MarcusHush theory, were compared to experimental data, with both theories parametrizing the data similarly well. An experimental value for the Marcusian parameter, 1 was also determined in all cases. For the reduction of 2-nitrotoluene, this was 0.5 +/- 0.1 eV in both solvents, while for NCP and BuN in [P-14,P-6,P-6,P-6][FAP], it was 2 +/- 0.1 and 5 +/- 0.1 eV, respectively. This is attributed to the localization of charge on the nitro group and the primary nitro alkyls increased interaction with the environment, resulting in a larger reorganization energy.

Original languageEnglish
Pages (from-to)3634-3647
Number of pages14
JournalJournal of Physical Chemistry C
Volume119
Issue number7
Early online date23 Jan 2015
DOIs
Publication statusPublished - 19 Feb 2015

Keywords

  • POTENTIAL-STEP CHRONOAMPEROMETRY
  • EXPONENTIALLY EXPANDING MESH
  • DIFFUSION-COEFFICIENTS
  • EFFICIENT SIMULATION
  • OXYGEN REDUCTION
  • EUROPIUM III
  • STEADY-STATE
  • VOLTAMMETRY
  • SOLVENTS
  • KINETICS

Cite this

@article{aef4780a5025418392b0caa9d24cac92,
title = "One-Electron Reduction of 2-Nitrotoluene, Nitrocyclopentane, and 1-Nitrobutane in Room Temperature Ionic Liquids: A Comparative Study of Butler–Volmer and Symmetric Marcus–Hush Theories Using Microdisk Electrodes",
abstract = "The voltammetry for the reduction of 2-nitrotoluene at a gold microdisk electrode is reported in two ionic liquids: trihexyltetradecylphosphonium tris(pentafluoroethyl)trifluorophosphate ([P-14,P-6,P-6,P-6][FAP]) and 1-ethyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([Emim][NTf2]). The reduction of nitrocyclopentane (NCP) and 1-nitrobutane (BuN) was investigated using voltammetry at a gold microdisk electrode in the ionic liquid [P-14,P-6,P-6,P-6][FAP]. Simulated voltammograms, generated through the use of ButlerVolmer theory and symmetric MarcusHush theory, were compared to experimental data, with both theories parametrizing the data similarly well. An experimental value for the Marcusian parameter, 1 was also determined in all cases. For the reduction of 2-nitrotoluene, this was 0.5 +/- 0.1 eV in both solvents, while for NCP and BuN in [P-14,P-6,P-6,P-6][FAP], it was 2 +/- 0.1 and 5 +/- 0.1 eV, respectively. This is attributed to the localization of charge on the nitro group and the primary nitro alkyls increased interaction with the environment, resulting in a larger reorganization energy.",
keywords = "POTENTIAL-STEP CHRONOAMPEROMETRY, EXPONENTIALLY EXPANDING MESH, DIFFUSION-COEFFICIENTS, EFFICIENT SIMULATION, OXYGEN REDUCTION, EUROPIUM III, STEADY-STATE, VOLTAMMETRY, SOLVENTS, KINETICS",
author = "Tanner, {Eden E. L.} and Barnes, {Edward O.} and Peter Goodrich and Christopher Hardacre and Compton, {Richard G.}",
year = "2015",
month = "2",
day = "19",
doi = "10.1021/jp512419d",
language = "English",
volume = "119",
pages = "3634--3647",
journal = "The Journal of Physical Chemistry C",
issn = "1932-7447",
publisher = "American Chemical Society",
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One-Electron Reduction of 2-Nitrotoluene, Nitrocyclopentane, and 1-Nitrobutane in Room Temperature Ionic Liquids: A Comparative Study of Butler–Volmer and Symmetric Marcus–Hush Theories Using Microdisk Electrodes. / Tanner, Eden E. L.; Barnes, Edward O.; Goodrich, Peter; Hardacre, Christopher; Compton, Richard G.

In: Journal of Physical Chemistry C, Vol. 119, No. 7, 19.02.2015, p. 3634-3647.

Research output: Contribution to journalArticle

TY - JOUR

T1 - One-Electron Reduction of 2-Nitrotoluene, Nitrocyclopentane, and 1-Nitrobutane in Room Temperature Ionic Liquids: A Comparative Study of Butler–Volmer and Symmetric Marcus–Hush Theories Using Microdisk Electrodes

AU - Tanner, Eden E. L.

AU - Barnes, Edward O.

AU - Goodrich, Peter

AU - Hardacre, Christopher

AU - Compton, Richard G.

PY - 2015/2/19

Y1 - 2015/2/19

N2 - The voltammetry for the reduction of 2-nitrotoluene at a gold microdisk electrode is reported in two ionic liquids: trihexyltetradecylphosphonium tris(pentafluoroethyl)trifluorophosphate ([P-14,P-6,P-6,P-6][FAP]) and 1-ethyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([Emim][NTf2]). The reduction of nitrocyclopentane (NCP) and 1-nitrobutane (BuN) was investigated using voltammetry at a gold microdisk electrode in the ionic liquid [P-14,P-6,P-6,P-6][FAP]. Simulated voltammograms, generated through the use of ButlerVolmer theory and symmetric MarcusHush theory, were compared to experimental data, with both theories parametrizing the data similarly well. An experimental value for the Marcusian parameter, 1 was also determined in all cases. For the reduction of 2-nitrotoluene, this was 0.5 +/- 0.1 eV in both solvents, while for NCP and BuN in [P-14,P-6,P-6,P-6][FAP], it was 2 +/- 0.1 and 5 +/- 0.1 eV, respectively. This is attributed to the localization of charge on the nitro group and the primary nitro alkyls increased interaction with the environment, resulting in a larger reorganization energy.

AB - The voltammetry for the reduction of 2-nitrotoluene at a gold microdisk electrode is reported in two ionic liquids: trihexyltetradecylphosphonium tris(pentafluoroethyl)trifluorophosphate ([P-14,P-6,P-6,P-6][FAP]) and 1-ethyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([Emim][NTf2]). The reduction of nitrocyclopentane (NCP) and 1-nitrobutane (BuN) was investigated using voltammetry at a gold microdisk electrode in the ionic liquid [P-14,P-6,P-6,P-6][FAP]. Simulated voltammograms, generated through the use of ButlerVolmer theory and symmetric MarcusHush theory, were compared to experimental data, with both theories parametrizing the data similarly well. An experimental value for the Marcusian parameter, 1 was also determined in all cases. For the reduction of 2-nitrotoluene, this was 0.5 +/- 0.1 eV in both solvents, while for NCP and BuN in [P-14,P-6,P-6,P-6][FAP], it was 2 +/- 0.1 and 5 +/- 0.1 eV, respectively. This is attributed to the localization of charge on the nitro group and the primary nitro alkyls increased interaction with the environment, resulting in a larger reorganization energy.

KW - POTENTIAL-STEP CHRONOAMPEROMETRY

KW - EXPONENTIALLY EXPANDING MESH

KW - DIFFUSION-COEFFICIENTS

KW - EFFICIENT SIMULATION

KW - OXYGEN REDUCTION

KW - EUROPIUM III

KW - STEADY-STATE

KW - VOLTAMMETRY

KW - SOLVENTS

KW - KINETICS

U2 - 10.1021/jp512419d

DO - 10.1021/jp512419d

M3 - Article

VL - 119

SP - 3634

EP - 3647

JO - The Journal of Physical Chemistry C

JF - The Journal of Physical Chemistry C

SN - 1932-7447

IS - 7

ER -