Electrochemical Reduction of 2,4-Dinitrotoluene in Room Temperature Ionic Liquids: A Mechanistic Investigation

© 2018 CSIRO. The reduction mechanism of 2,4-dinitrotoluene (DNT) has been studied in eight room temperature ionic liquids (RTILs) using cyclic voltammetry (CV), square wave voltammetry (SWV), chronoamperometry, and digital simulation. Two distinctive peaks are observed in the voltammetry, correspon...

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Main Authors: Lee, Wade, Hay, C., Silvester, Debbie
Format: Journal Article
Published: CSIRO Publishing 2018
Online Access:https://www.publish.csiro.au/ch/pdf/CH18315
http://hdl.handle.net/20.500.11937/71458
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author Lee, Wade
Hay, C.
Silvester, Debbie
author_facet Lee, Wade
Hay, C.
Silvester, Debbie
author_sort Lee, Wade
building Curtin Institutional Repository
collection Online Access
description © 2018 CSIRO. The reduction mechanism of 2,4-dinitrotoluene (DNT) has been studied in eight room temperature ionic liquids (RTILs) using cyclic voltammetry (CV), square wave voltammetry (SWV), chronoamperometry, and digital simulation. Two distinctive peaks are observed in the voltammetry, corresponding to the stepwise reduction of the two nitro groups on the aromatic ring. Diffusion coefficients (D) and electron counts (n) were calculated from chronoamperometric transients, revealing an electron count of one in most RTILs, and a linear relationship between D and the inverse of viscosity. Focusing on the first reduction only, the peak appears to be chemically reversible at low concentrations. However, as the concentration increases, the current of the reverse peak diminishes, suggesting that one or more chemical steps occur after the electrochemical step. The results from digital simulation of the CVs in one of the RTILs reveal that the most likely mechanism involves a deprotonation of the methyl group of a parent DNT molecule by the electrogenerated radical anion and/or a dimerisation of two electrogenerated radical anions. Elucidation of the reduction mechanism of DNT (and other explosives) is vital if electrochemical techniques are to be employed to detect these types of compounds in the field.
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publishDate 2018
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spelling curtin-20.500.11937-714582023-04-26T05:30:28Z Electrochemical Reduction of 2,4-Dinitrotoluene in Room Temperature Ionic Liquids: A Mechanistic Investigation Lee, Wade Hay, C. Silvester, Debbie © 2018 CSIRO. The reduction mechanism of 2,4-dinitrotoluene (DNT) has been studied in eight room temperature ionic liquids (RTILs) using cyclic voltammetry (CV), square wave voltammetry (SWV), chronoamperometry, and digital simulation. Two distinctive peaks are observed in the voltammetry, corresponding to the stepwise reduction of the two nitro groups on the aromatic ring. Diffusion coefficients (D) and electron counts (n) were calculated from chronoamperometric transients, revealing an electron count of one in most RTILs, and a linear relationship between D and the inverse of viscosity. Focusing on the first reduction only, the peak appears to be chemically reversible at low concentrations. However, as the concentration increases, the current of the reverse peak diminishes, suggesting that one or more chemical steps occur after the electrochemical step. The results from digital simulation of the CVs in one of the RTILs reveal that the most likely mechanism involves a deprotonation of the methyl group of a parent DNT molecule by the electrogenerated radical anion and/or a dimerisation of two electrogenerated radical anions. Elucidation of the reduction mechanism of DNT (and other explosives) is vital if electrochemical techniques are to be employed to detect these types of compounds in the field. 2018 Journal Article http://hdl.handle.net/20.500.11937/71458 10.1071/CH18315 https://www.publish.csiro.au/ch/pdf/CH18315 http://purl.org/au-research/grants/arc/FT170100315 CSIRO Publishing unknown
spellingShingle Lee, Wade
Hay, C.
Silvester, Debbie
Electrochemical Reduction of 2,4-Dinitrotoluene in Room Temperature Ionic Liquids: A Mechanistic Investigation
title Electrochemical Reduction of 2,4-Dinitrotoluene in Room Temperature Ionic Liquids: A Mechanistic Investigation
title_full Electrochemical Reduction of 2,4-Dinitrotoluene in Room Temperature Ionic Liquids: A Mechanistic Investigation
title_fullStr Electrochemical Reduction of 2,4-Dinitrotoluene in Room Temperature Ionic Liquids: A Mechanistic Investigation
title_full_unstemmed Electrochemical Reduction of 2,4-Dinitrotoluene in Room Temperature Ionic Liquids: A Mechanistic Investigation
title_short Electrochemical Reduction of 2,4-Dinitrotoluene in Room Temperature Ionic Liquids: A Mechanistic Investigation
title_sort electrochemical reduction of 2,4-dinitrotoluene in room temperature ionic liquids: a mechanistic investigation
url https://www.publish.csiro.au/ch/pdf/CH18315
https://www.publish.csiro.au/ch/pdf/CH18315
http://hdl.handle.net/20.500.11937/71458