Isotopic enrichments via altered first and second solution electron affinities

Journal Article · Wed Sep 17 04:00:00 EDT 1986 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00279a016· OSTI ID:5342660

Stevenson, G R; Espe, M P; Reiter, R C

Electron spin resonance experiments have been utilized to show that the solution electron affinity of benzene-/sup 13/C/sub 6/ is less than that of benzene by 0.24 kcal/mol and that the solution EA of benzene-d/sub 6/ is less than that of benzene by 0.44 kcal/mol. Perdeuteration of naphthalene, anthracene, or perylene results in a very similar lowering of the solution EA of the hydrocarbon as evidenced by the fact that the equilibrium constant for the electron transfer between the hydrocarbon anion radical, X/sup .-/, and the perdeuterated hydrocarbon, Xd (X/sup .-/ + Xd = Xd/sup .-/ + X), is less than unity. Likewise the second EAs of perdeuterated perylene and anthracene are lower than those of the unsubstituted hydrocarbons (K/sub eq/ for X/sup 2 -/ + Xd/sup .-/ = X/sup .-/ + Xd/sup 2 -/ is less than unity). The free energy and enthalpy of electron transfer from the anthracene anion radical to perdeuterated anthracene is 0.41 kcal/mol and that from the anthracene dianion to the perdeuterated anion radical is 0.10 kcal/mol. The fact that these equilibrium constants are not equal to 1 enables one to use the difference in the chemical reactivity of the ions and neutral molecules to selectively isotopically enrich the hydrocarbons involved.

• Research Organization: Illinois State Univ., Normal
• OSTI ID: 5342660
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 108:19; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400303* -- Organic Chemistry-- Isotope Exchange & Isotope Separation-- (-1987)
AFFINITY
ANTHRACENE
AROMATICS
BENZENE
CARBON 12
CARBON 13
CARBON ISOTOPES
CONDENSED AROMATICS
DATA
DEUTERIUM
ELECTRON SPIN RESONANCE
ELEMENTS
EVEN-EVEN NUCLEI
EVEN-ODD NUCLEI
EXPERIMENTAL DATA
HYDROCARBONS
HYDROGEN
HYDROGEN ISOTOPES
INFORMATION
ISOTOPE SEPARATION
ISOTOPES
LIGHT NUCLEI
MAGNETIC RESONANCE
NAPHTHALENE
NONMETALS
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
PERYLENE
RESONANCE
SEPARATION PROCESSES
STABLE ISOTOPES