Oxidation of glyoxylic acid by cerium(IV): Oxygen-induced enhancement of the primary radical concentration

Journal Article · Thu Jul 25 00:00:00 EDT 1996 · Journal of Physical Chemistry

DOI:https://doi.org/10.1021/jp960300w· OSTI ID:380804

Neumann, B ^[1]; Steinbock, O; Dalal, N S ^[2]; Mueller, S C ^[1]

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1. Max-Planck-Institut fuer Molekulare Physiologie, Dortmund (Germany)
2. Florida State Univ., Tallahassee, FL (United States)

In order to help understand the role of oxygen in Ce(IV)-induced oxidation of small carbonic acids, we investigated the reaction of glyoxylic acid (HCOCOOH) and Ce(IV) in 1 M sulfuric acid. Spectrophotometric data showed that in excess of glyoxylic acid the consumption of Ce(IV) obeys pseudo-first-order kinetics, with a rate constant of 8.8 L mol{sup -1} s{sup -1} at 25{degree}C and an activation energy of 80 kJ mol{sup -1}. Rapid-flow EPR measurements revealed an approximately 1:2:1 triplet with a g value of 2.0071{+-}0.0005 and a hyperfine splitting of 7.1{+-}0.2 G, assignable to the primary radical formed by abstraction of a hydrogen atom from hydrated glyoxylic acid. The rate constant for the anaerobic self-decay of the radical was measured as approximately 3.7x10{sup 9} L mol{sup -1} s{sup -1}. Surprisingly, oxygen had no effect on the Ce(IV) kinetics, while the radical decay was significantly inhibited under aerobic conditions (ratio of experimental rate constants = 6.3). Amperometric measurements revealed accompanying oxygen consumption. Analyses based on numerical simulations show that the observed oxygen-induced increase in radical concentration cannot be explained in the framework of standard autooxidation mechanisms. An alternative reaction scheme is suggested which reproduces the observed aerobic radical kinetics and which thus could be relevant to similar oxidation reactions. 30 refs., 7 figs., 2 tabs.

• OSTI ID: 380804
• Journal Information: Journal of Physical Chemistry, Vol. 100, Issue 30; Other Information: PBD: 25 Jul 1996
• Country of Publication: United States
• Language: English

Related Subjects

40 CHEMISTRY
36 MATERIALS SCIENCE
99 MATHEMATICS
COMPUTERS
INFORMATION SCIENCE
MANAGEMENT
LAW
MISCELLANEOUS
GLYOXYLIC ACID
OXIDATION
CATALYSIS
CHEMICAL REACTION KINETICS
ACTIVATION ENERGY
ORGANIC ACIDS
RADICALS
ABUNDANCE
CARBONIC ACID
CERIUM
CATALYSTS
NUMERICAL ANALYSIS
ELECTRON SPECTRA
ELECTRON SPIN RESONANCE