Kinetic isotope effects for hydrogen abstractions from n-alkanes by hydrogen atoms in the gas phase
Kinetic isotope effects k/sub H//k/sub D/ for the reactions H/sup bullet/+n-C/sub n/H/sub 2n/+2(n-C/sub n/D/sub 2n/+2) ..-->../sup k//sub H//sup( k//sub D/)/sup /H/sub 2/(HD)+C/sub n/ H/sup bullet//sub 2n/+1(C/sub n/D/sup bullet//sub 2n/+1) have been measured using hydrogen atoms produced in the radiolysis of water vapor. The normal alkanes investigated were n-hexane, n-heptane, n-octane, n-nonane, and n-decane. Regardless of the chain lengths of the n-alkanes studied, the results can be expressed within the experimental error with an Arrhenius type equation k/sub H//k/sub D/ = (0.47 +- 0.03) exp ((9.41 +- 0.21) kJ mol/sup -1//RT) over the temperature range of 363--463 K. The experimental results were compared with theoretical calculations using transition-state theory and the London--Eyring--Polanyi--Sato (LEPS) potential-energy surface. Good agreement between experimental and calculated values was obtained when allowance was made for tunneling effects.
- Research Organization:
- Institute of Physical Chemistry, Federal School of Technology, CH-1015 Lausanne, Switzerland
- OSTI ID:
- 5152024
- Journal Information:
- J. Chem. Phys.; (United States), Vol. 80:6
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ALKANES
CHEMICAL REACTION KINETICS
DEUTERIUM
ISOTOPE EFFECTS
HYDROGEN
ARRHENIUS EQUATION
ELEMENTS
EQUATIONS
HYDROCARBONS
HYDROGEN ISOTOPES
ISOTOPES
KINETICS
LIGHT NUCLEI
NONMETALS
NUCLEI
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
REACTION KINETICS
STABLE ISOTOPES
400302* - Organic Chemistry- Isotope Effects- (-1987)