ESR study of electron reactions with carboxylic acids, ketones, and aldehydes in aqueous glasses
Electron reactions with a number of carboxylic acids, ketones, and aldehydes were investigated in a deuterated neutral aqueous glass at 77 K by ESR spectroscopy. Free radical reactions which took place upon warming the glasses to temperatures at which the electron adducts become mobile were studied. For carboxylic acids (C/sub n/H/sub 2n+1/CO/sub 2/D, n = 2,3) the deuterated anion radicals (RCH/sub 2/C(OD)/sub 2/) give results which suggest abstraction of a hydrogen from the parent acid to produce radicals of structure RCHCO/sub 2/D. The formic acid deuterated anion is found to undergo a similar mechanism. The acetic acid deuterated anion is not found to abstract from acetic acid, but is found to abstract from isopropyl alcohol. Ketone electron adducts are also found to abstract from their parent compounds to yield radicals of structure RCHC(O)R' with R and R' = CH/sub 3/, C/sub 2/H/sub 5/. Electron reactions with five aldehydes (RCHO with R = H, CH/sub 3/, C/sub 2/H/sub 5/, C/sub 3/H/sub 7/, and i-C/sub 3/H/sub 7/) gave their corresponding alcohol radicals (RCHOD) after deuteration at 77 K. Radicals with R = C/sub 2/H/sub 5/, C/sub 3/H/sub 7/, and i-C/sub 3/H/sub 7/ were found to abstract from the parent aldehyde to form radicals of structure RR'CCHO. The methanol radical (CH/sub 2/OD) showed no further reaction while the ethanol radical (CH/sub 3/CHOD) resulted in the production of the diacetal anion. The results for acids, aldehydes, and ketones show that radicals of structure RC(OD)R' with R' = OD, H, or an alkyl group can act as hydrogen atom abstracting agents.
- Research Organization:
- Oakland Univ., Rochester, MI
- OSTI ID:
- 6417813
- Journal Information:
- J. Phys. Chem.; (United States), Vol. 85:7
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ALDEHYDES
PHOTOLYSIS
CARBOXYLIC ACIDS
KETONES
AQUEOUS SOLUTIONS
DEUTERIUM COMPOUNDS
ELECTRON ATTACHMENT
ELECTRON SPIN RESONANCE
FERROCYANIDES
GLASS
LITHIUM CHLORIDES
LOW TEMPERATURE
RADICALS
ALKALI METAL COMPOUNDS
CHEMICAL REACTIONS
CHLORIDES
CHLORINE COMPOUNDS
COMPLEXES
DECOMPOSITION
DISPERSIONS
HALIDES
HALOGEN COMPOUNDS
HYDROGEN COMPOUNDS
IRON COMPLEXES
LITHIUM COMPOUNDS
LITHIUM HALIDES
MAGNETIC RESONANCE
MIXTURES
ORGANIC ACIDS
ORGANIC COMPOUNDS
PHOTOCHEMICAL REACTIONS
RESONANCE
SOLUTIONS
TRANSITION ELEMENT COMPLEXES
400500* - Photochemistry