Electrochemistry of nitrobenzene and p-nitrobenzaldehyde studied by transmission spectroelectrochemical methods in sulfolane
Journal Article
·
· J. Phys. Chem.; (United States)
- Univ. of New Mexico, Albuquerque
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 E/sub p.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 (epsilon 5.7 x 10/sup 3/ M/sup -1/ cm/sup -1/) and 465 nm (epsilon 4.1 x 10/sup 3/ M/sup -1/ cm/sup -1/). p-Nitrobenzaldehyde undergoes two one-electron reductions (E/sub p,1/ = -1.528 V, E/sub p,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 (k/sub f/ = 5.4 +- 0.7 x 10/sup 2/ M/sup -1/ s/sup -1/ at 50/sup 0/C). Verification of the proposed mechanism is assisted by digital simulation techniques and a newly developed differential treatment of the spectroelectrochemical data.
- OSTI ID:
- 7336582
- Journal Information:
- J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Journal Issue: 25 Vol. 80:25; ISSN JPCHA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400400* -- Electrochemistry
ABSORPTION SPECTRA
ALDEHYDES
AROMATICS
CHEMISTRY
ELECTROCHEMISTRY
HETEROCYCLIC COMPOUNDS
NITRO COMPOUNDS
NITROBENZENE
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
ORGANIC SULFUR COMPOUNDS
SPECTRA
400400* -- Electrochemistry
ABSORPTION SPECTRA
ALDEHYDES
AROMATICS
CHEMISTRY
ELECTROCHEMISTRY
HETEROCYCLIC COMPOUNDS
NITRO COMPOUNDS
NITROBENZENE
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
ORGANIC SULFUR COMPOUNDS
SPECTRA