Deuterium solvent isotope effect on the basicity of methanol. Deuterium fractionation factor for CH/sub 3/OL/sub 2//sup +/ in aqueous solution

Journal Article · Thu Feb 13 00:00:00 EST 1986 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100276a008· OSTI ID:5826225

Kurz, J L; Hazen, S L; Kurz, L C

The H/sub 2/O/D/sub 2/O solvent isotope effect on the acid dissociation constant for CH/sub 2/OL/sub 2//sup +/ has been measured by /sup 13/C NMR. Its value, K/sub a//sup H//k/sub a//sup D/ = 0.95 +/- 0.02 near 20 /sup 0/C, was obtained as the ratio of the initial slopes of plots of /sup 13/delta vs. (H/sup +/) in H/sub 2/O and vs. (D/sup +/) in D/sub 2/O. The corresponding value of the deuterium fractionation factor for CH/sub 3/OL/sub 2//sup +/ relative to L/sub 2/O in water is 0.58 +/- 0.03. Comparison to the fractionation factor for L/sub 2/O/sup +/ (0.69) shows that methyl substitution significantly increases the ability of the OL/sup +/ site to select between H and D. 17 references, 1 figure, 1 table.

• Research Organization: Washington Univ., St. Louis, MO
• OSTI ID: 5826225
• Journal Information: J. Phys. Chem.; (United States), Vol. 90:4
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
DEUTERIUM COMPOUNDS
ISOTOPE EFFECTS
HEAVY WATER
AQUEOUS SOLUTIONS
METHYL RADICALS
DEUTERATION
WATER
CARBON 13
CHEMICAL REACTION KINETICS
DISSOCIATION
EXPERIMENTAL DATA
NUCLEAR MAGNETIC RESONANCE
QUANTITY RATIO
ALKYL RADICALS
CARBON ISOTOPES
CHEMICAL REACTIONS
DATA
DISPERSIONS
EVEN-ODD NUCLEI
HYDROGEN COMPOUNDS
INFORMATION
ISOTOPES
KINETICS
LIGHT NUCLEI
MAGNETIC RESONANCE
MIXTURES
NUCLEI
NUMERICAL DATA
OXYGEN COMPOUNDS
RADICALS
REACTION KINETICS
RESONANCE
SOLUTIONS
STABLE ISOTOPES
400302* - Organic Chemistry- Isotope Effects- (-1987)