Isotopic exchange reactions of amines. II. Amino-amide proton exchange in the potassium methylamide-methylamine system
Journal Article
·
· J. Phys. Chem.; (United States)
The kinetics of the methylamine-potassium methylamide amino proton exchange reaction were studied by /sup 1/H NMR as a function of temperature and catalyst concentration. Rates were determined by analysis of the line shapes of both the amino and methyl peaks. The exchange kinetics cannot be described by a single bimolecular rate constant based on solvent and stoichiometric amide concentration. By using published data for the dissociation constant of potassium methylamide in methylamine, we calculated bimolecular rate constants for two cataytically active species in solution: free methylamide ions and potassium methylamide ion pairs. These are at 25/sup 0/C as follows: k/sub 2/(free ion) = 1.42 x 10/sup 9/ L.mol/sup -1/.s/sup -1/, k/sub 2/(ion pair) = 1.04 x 10/sup 8/ L.mol/sup -1/.s/sup -1/, with activation parameters ..delta..H double dagger = 12.8 and 10.3 kJ.mol/sup -1/ and ..delta..S double dagger = -27 and -57 J.mol/sup -1/.K/sup -1/, respectively. The NMR spectrum of anhydrous methylamine was recorded as a function of temperature over the range -82 to +75/sup 0/C. Values of 46.7 and 7.0/sub 4/ Hz, respectively, were found for the /sup 14/N-H and H-N-C-H spin coupling constants in methylamine. In addition the spin lifetimes of the methylamine /sup 14/N yielded an activation energy for quadrupole relaxation, a parameter characterizing rotational diffusion in the liquid phase, of 8.7 kJ.mol/sup -1/. 8 figures, 3 tables.
- Research Organization:
- Atomic Energy of Canada Limited, Chalk River, Ontario
- OSTI ID:
- 6255433
- Journal Information:
- J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 83:14; ISSN JPCHA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400303* -- Organic Chemistry-- Isotope Exchange & Isotope Separation-- (-1987)
ACTIVATION ENERGY
ALKALI METAL COMPOUNDS
AMIDES
AMINES
ANGULAR MOMENTUM
CHEMICAL REACTION KINETICS
DATA
DEUTERIUM
ENERGY
EXPERIMENTAL DATA
HYDROGEN ISOTOPES
INFORMATION
ISOTOPES
ISOTOPIC EXCHANGE
KINETICS
LIGHT NUCLEI
LOW TEMPERATURE
MAGNETIC RESONANCE
MEDIUM TEMPERATURE
NUCLEAR MAGNETIC RESONANCE
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PARTICLE PROPERTIES
POTASSIUM COMPOUNDS
REACTION KINETICS
RESONANCE
SPIN
STABLE ISOTOPES
400303* -- Organic Chemistry-- Isotope Exchange & Isotope Separation-- (-1987)
ACTIVATION ENERGY
ALKALI METAL COMPOUNDS
AMIDES
AMINES
ANGULAR MOMENTUM
CHEMICAL REACTION KINETICS
DATA
DEUTERIUM
ENERGY
EXPERIMENTAL DATA
HYDROGEN ISOTOPES
INFORMATION
ISOTOPES
ISOTOPIC EXCHANGE
KINETICS
LIGHT NUCLEI
LOW TEMPERATURE
MAGNETIC RESONANCE
MEDIUM TEMPERATURE
NUCLEAR MAGNETIC RESONANCE
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PARTICLE PROPERTIES
POTASSIUM COMPOUNDS
REACTION KINETICS
RESONANCE
SPIN
STABLE ISOTOPES