Kinetics of the reactions of unsaturated hydrocarbon free radicals (vinyl, allyl, and propargyl) with molecular chlorine

Journal Article · Thu Mar 26 04:00:00 EST 1987 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100291a037· OSTI ID:6631062

Timonen, R S; Russell, J J; Sarzynski, D; Gutman, D

The kinetics of the reactions of three unsaturated free radicals (vinyl, allyl, and propargyl) with molecular chlorine have been studied by using a tubular reactor coupled to a photoionization mass spectrometer. The radicals were homogeneously generated by the pulsed photolysis of precursor molecules at 193 nm. The subsequent decays of the radical concentrations were monitored in real-time experiments as a function of Cl/sub 2/ concentration to obtain the rate constants of these Cl atom metathesis reactions. Rate constants were measured as a function of temperature to obtain Arrhenius parameters. The following rate constant expressions were obtained (units of the preexponential factor are cm/sup 3/ molecule/sup -1/ s/sup -1/, and activation energies are in kJ mol/sup -1/; the temperature range covered in each study is also indicated): C/sub 2/H/sub 3/ + Cl/sub 2/ )10/sup -11.06/ exp(2/RT), 298-435 K); C/sub 3/H/sub 3/ + Cl/sub 2/ )10/sup -10.56/ exp(-28/RT), 525-693 K); C/sub 3/H/sub 5/ + Cl/sub 2/ )10/sup -10.81/ exp(-18/RT), 487-693 K). The factors governing the reactivity of polyatomic free radicals in these and other Cl atom transfer reactions with molecular chlorine are reviewed.

• Research Organization: Illinois Institute of Technology, Chicago
• OSTI ID: 6631062
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 91:7; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400500 -- Photochemistry
ALKYL RADICALS
ALLYL RADICALS
ARRHENIUS EQUATION
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHLORINE
DATA
DECOMPOSITION
ELEMENTS
EQUATIONS
EXPERIMENTAL DATA
HALOGENS
INFORMATION
KINETICS
MASS SPECTROSCOPY
NONMETALS
NUMERICAL DATA
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
PROPARGYL RADICALS
RADICALS
REACTION KINETICS
SPECTROSCOPY
VINYL RADICALS