The electrochemistry of nitrobenzene and p-nitrobenzaldehyde studied by transmission spectroelectrochemical methods in sulfolane

Neal R Armstrong, N. E. Vanderborgh, Rod K. Quinn

Research output: Contribution to journalArticle

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Abstract

Transmission spectroelectrochemistry experiments have been used to study the electrochemical reductions of nitrobenzene and p-nitrobenzaldehyde in sulfolane. The reduction intermediates of both these aromatic compounds are sufficiently long-lived in sulfolane to be amenable to study by these techniques. Nitrobenzene undergoes a single one-electron, chemically reversible reduction at Ep,c = -1.875 V vs. AgRE. This was verified by analysis of the visible absorption spectrum for the reduction species; two maxima were observed at 348 nm (ε 5.7 × 103 M-1 cm-1) and 465 nm (ε 4.1 × 103 M-1 cm-1). p-Nitrobenzaldehyde undergoes two one-electron reductions (Ep,1 = -1.528 V, Ep,2 = -2.114 V vs. AgRE), which are accompanied by following chemical reactions. A mechanism is shown involving formation of a parent-radical anion complex and an unusually low reproportionation reaction rate (kf = 5.4 ± 0.7 × 102 M-1 s-1 at 50°C). Verification of the proposed mechanism is assisted by digital simulation techniques and a newly developed differential treatment of the spectroelectrochemical data.

Original languageEnglish (US)
Pages (from-to)2740-2745
Number of pages6
JournalJournal of Physical Chemistry
Volume80
Issue number25
StatePublished - 1976
Externally publishedYes

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Nitrobenzene
nitrobenzenes
Electrochemistry
electrochemistry
digital simulation
aromatic compounds
Spectroelectrochemistry
visible spectrum
Electrons
Aromatic compounds
chemical reactions
reaction kinetics
electrons
Reaction rates
Anions
Absorption spectra
Chemical reactions
anions
absorption spectra
Negative ions

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

The electrochemistry of nitrobenzene and p-nitrobenzaldehyde studied by transmission spectroelectrochemical methods in sulfolane. / Armstrong, Neal R; Vanderborgh, N. E.; Quinn, Rod K.

In: Journal of Physical Chemistry, Vol. 80, No. 25, 1976, p. 2740-2745.

Research output: Contribution to journalArticle

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AB - Transmission spectroelectrochemistry experiments have been used to study the electrochemical reductions of nitrobenzene and p-nitrobenzaldehyde in sulfolane. The reduction intermediates of both these aromatic compounds are sufficiently long-lived in sulfolane to be amenable to study by these techniques. Nitrobenzene undergoes a single one-electron, chemically reversible reduction at Ep,c = -1.875 V vs. AgRE. This was verified by analysis of the visible absorption spectrum for the reduction species; two maxima were observed at 348 nm (ε 5.7 × 103 M-1 cm-1) and 465 nm (ε 4.1 × 103 M-1 cm-1). p-Nitrobenzaldehyde undergoes two one-electron reductions (Ep,1 = -1.528 V, Ep,2 = -2.114 V vs. AgRE), which are accompanied by following chemical reactions. A mechanism is shown involving formation of a parent-radical anion complex and an unusually low reproportionation reaction rate (kf = 5.4 ± 0.7 × 102 M-1 s-1 at 50°C). Verification of the proposed mechanism is assisted by digital simulation techniques and a newly developed differential treatment of the spectroelectrochemical data.

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