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Title: 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}
}