Deuterium isotope exchange between molecular hydrogen and cyclohexylamine
Deuterium isotope exchange between molecular hydrogen and cyclohexylamine (CHA) has been studied by using the LiCHA, NaCHA, KCHA, and CsCHA salts as catalysts in a stirred reactor over the temperature range -15 to + 15/sup 0/C. The reaction in solution is very fast (comparable to the amide/ammonia and methylamide/methylamine systems), and even at -15/sup 0/C (CHA fp -17.8/sup 0/C) rate constants independent of mass transfer could be obtained only for the Li and Na salts in the present apparatus. For these, the kinetic isotope effect (k.i.e., 1.7 to 2.0) and activation parameter (E/sub a/, 11-17 kJ.mol/sup -1/) data have been compared with literature values for base-catalyzed exchange with other protic solvents. Reasons for the observed relative catalyst reactivity LiCH much less than NaCHA < KCHA < CsCHA are considered. It has been found that, under some experimental conditions, mass transfer effects can lead to an incorrect k.i.e. value when this is derived from data for a single kinetic run D/sub 2/ ..-->.. HD ..-->.. H/sub 2/. The solubility of H/sub 2/ in CHA has been measured over the temperature range -15 to +15/sup 0/C. 50 references, 5 figures, 2 tables.
- Research Organization:
- Atomic Energy of Canada Ltd., Ontario
- OSTI ID:
- 5772885
- Journal Information:
- J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 101:22; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400301 -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
400303* -- Organic Chemistry-- Isotope Exchange & Isotope Separation-- (-1987)
ACTIVATION ENERGY
ALKALI METAL COMPOUNDS
ALKANES
AMINES
CATALYSTS
CATALYTIC EFFECTS
CESIUM COMPOUNDS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CRYOGENIC FLUIDS
CYCLOALKANES
DATA
DATA FORMS
DEUTERIUM
ELEMENTS
ENERGY
EXPERIMENTAL DATA
FLUIDS
HYDROCARBONS
HYDROGEN
HYDROGEN ISOTOPES
INFORMATION
ISOLATED VALUES
ISOTOPES
ISOTOPIC EXCHANGE
KINETICS
LABELLING
LIGHT NUCLEI
LITHIUM COMPOUNDS
LOW TEMPERATURE
MASS TRANSFER
MEDIUM TEMPERATURE
NONMETALS
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
POTASSIUM COMPOUNDS
REACTION KINETICS
REACTIVITY
SALTS
SODIUM COMPOUNDS
SOLUBILITY
STABLE ISOTOPES
TEMPERATURE DEPENDENCE