Isotope effects in proton-transfer reactions. An ion cyclotron resonance determination of the equilibrium deuterium isotope effect in the bichloride ion
The equilibrium constant for the gas-phase chloride exchange reaction ClHCl/sup -/ + DCl in equilibrium ClDCl/sup -/ + HCl has been measured by using ion cyclotron resonance spectroscopic trapped-ion techniques. The value obtained of 0.60 can be shown by statistical thermodynamic calculations to be principally due to rotational partition function ratios rather than due to differences in zero-point energies. The equilibrium data have been used to calculate a gas-phase deuterium fractionation factor of 0.28, inferring that the bichloride ion should have a double-minimum potential energy well with the lowest allowed energy level at or near the height of the central barrier. Implications for kinetic isotope effects are also discussed.
- Research Organization:
- Univ. of Waterloo, Ontario
- OSTI ID:
- 6949221
- Journal Information:
- J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 91:3; ISSN JPCHA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400202* -- Isotope Effects
Isotope Exchange
& Isotope Separation
ANIONS
CHARGED PARTICLES
CHEMICAL REACTION KINETICS
CHLORINE COMPOUNDS
DATA
DEUTERIUM
DEUTERIUM COMPOUNDS
ENERGY
EXPERIMENTAL DATA
HALOGEN COMPOUNDS
HYDROGEN COMPOUNDS
HYDROGEN ISOTOPES
HYDROGEN TRANSFER
INFORMATION
IONS
ISOTOPE EFFECTS
ISOTOPES
KINETICS
LIGHT NUCLEI
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
PHASE TRANSFORMATIONS
POTENTIAL ENERGY
REACTION KINETICS
STABLE ISOTOPES