Kinetic isotope effects for hydrogen abstractions from n-alkanes by hydrogen atoms in the gas phase
Abstract
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.
- Authors:
- Publication Date:
- Research Org.:
- Institute of Physical Chemistry, Federal School of Technology, CH-1015 Lausanne, Switzerland
- OSTI Identifier:
- 5152024
- Resource Type:
- Journal Article
- Journal Name:
- J. Chem. Phys.; (United States)
- Additional Journal Information:
- Journal Volume: 80:6
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, 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)
Citation Formats
Fujisaki, N, Ruf, A, and Gaeumann, T. Kinetic isotope effects for hydrogen abstractions from n-alkanes by hydrogen atoms in the gas phase. United States: N. p., 1984.
Web. doi:10.1063/1.447050.
Fujisaki, N, Ruf, A, & Gaeumann, T. Kinetic isotope effects for hydrogen abstractions from n-alkanes by hydrogen atoms in the gas phase. United States. https://doi.org/10.1063/1.447050
Fujisaki, N, Ruf, A, and Gaeumann, T. 1984.
"Kinetic isotope effects for hydrogen abstractions from n-alkanes by hydrogen atoms in the gas phase". United States. https://doi.org/10.1063/1.447050.
@article{osti_5152024,
title = {Kinetic isotope effects for hydrogen abstractions from n-alkanes by hydrogen atoms in the gas phase},
author = {Fujisaki, N and Ruf, A and Gaeumann, T},
abstractNote = {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.},
doi = {10.1063/1.447050},
url = {https://www.osti.gov/biblio/5152024},
journal = {J. Chem. Phys.; (United States)},
number = ,
volume = 80:6,
place = {United States},
year = {Thu Mar 15 00:00:00 EST 1984},
month = {Thu Mar 15 00:00:00 EST 1984}
}