Infrared chemiluminescence studies of the reaction of fluorine atoms with monosubstituted ethylene compounds

The technique of arrested relaxation infrared chemiluminescence has been utilized for the observation of emission from the polyatomic substitution products of fluorine atom reactions with ethylene, propene, vinyl chloride, and vinyl bromide. A new apparatus for performing such experiments is described. The entire apparatus, including the scanning Michelson interferometer used in obtaining the emission spectra, is cooled to liquid nitrogen temperatures or lower. The resulting improvement in signal to noise ratio allows emission spectra to be recorded down to frequencies as low as 720 cm−1. Analysis of the chemiluminescence data allows the determination of the partitioning of reaction energy over the product vibrational modes. The results indicate statistical partitioning occurs for the vinyl chloride and bromide reactions, while the ethylene and propene reactions exhibit nonstatistical partitioning. The difference in energy partitioning for these reactions is attributed to the existence of a potential ener...

[1]  J. D. Mcdonald,et al.  Molecular beam chemistry. Unimolecular decomposition of chemically activated chlorobromoalkyl radicals , 1973 .

[2]  K. C. Kim,et al.  Hydrogen fluoride and deuterium fluoride infrared chemiluminescence and energy partitioning from the reactions of fluorine atoms with C6-C10 cycloalkanes and propane-d6 , 1973 .

[3]  S. Rice,et al.  Unimolecular decomposition of the long‐lived complex formed in the reaction F+C4H8 , 1973 .

[4]  J. Kochi,et al.  Structure and conformation of -chloroalkyl radicals , 1973 .

[5]  D. Setser,et al.  Infrared chemiluminescence and energy partitioning from reactions of fluorine atoms with hydrides of carbon, silicon, oxygen, sulfur, nitrogen, and phosphorus , 1973 .

[6]  J. Polanyi,et al.  Energy Distribution Among Reaction Products. V. H + X2 (X ≡ Cl, Br), D + Cl2 , 1972 .

[7]  D. H. Maylotte,et al.  Energy Distribution Among Reaction Products. IV. X+HY (X ≡ Cl, Br; Y ≡ Br, I), Cl+DI , 1972 .

[8]  J. J. Sloan,et al.  Energy Distribution Among Reaction Products. VI. F+H2, D2 , 1972 .

[9]  Ian W. M. Smith,et al.  Quenching of Infrared Chemiluminescence: Rates of Energy Transfer from HF (v ≤ 5) to CO2 and HF, and from DF (v ≤ 3) to CO2 and HF , 1972 .

[10]  J. Polanyi,et al.  Energy Distribution Among Reaction Products. VI. F+H 2 , D 2 , 1972 .

[11]  J. Parson,et al.  Crossed Molecular Beam Study of F+C2H4, C2D4 , 1972 .

[12]  J. Polanyi,et al.  Formation of Vibrationally Excited OH by the Reaction H + O(3). , 1971, Applied optics.

[13]  Irl W. Smith,et al.  Quenching of Infrared Chemiluminescence. 1: The Rates of De-Excitation of CO (4 , 1971, Applied optics.

[14]  D. Herschbach,et al.  Molecular Beam Electric Resonance Spectra of Reaction Products: Vibrational Energy Distribution in CsF from Cs+SF6 , 1971 .

[15]  J. Polanyi,et al.  Location of Energy Barriers. III. Effect on the Dynamics of Reactions AB + CD → AC + BD , 1970 .

[16]  J. Polanyi,et al.  Vibrational energy distribution in HF formed by elimination from activated CH3CF3 and CH2CF2 , 1970 .

[17]  B. Rabinovitch,et al.  Collisional transition probability distributions for deactivation of vibrationally excited dimethylcyclopropane , 1970 .

[18]  P. N. Clough,et al.  Formation of vibrationally excited N2O in the reaction of nitrogen atoms with NO2 , 1969, Proceedings of the Royal Society of London. A. Mathematical and Physical Sciences.

[19]  J. L. Franklin,et al.  Correlation of Excess Energies of Electron‐Impact Dissociations with the Translational Energies of the Products , 1968 .

[20]  G. Whitten,et al.  Vibration‐Rotation Energy‐Level Density Calculations , 1968 .

[21]  Lester Andrews,et al.  Infrared Spectrum of the Methyl Radical in Solid Argon , 1967 .

[22]  R. Irwin,et al.  Rates of Addition of Methyl Radicals to Olefins in the Gas Phase , 1967 .

[23]  Janine Connes,et al.  Near-infrared planetary spectra by Fourier spectroscopy. I. Instruments and results (Journal of the Optical Society of America 1966) , 1966 .

[24]  P. Kebarle,et al.  Addition of Methyl Radicals to Vinyl Chloride and Catalysis of Di-t-butyl Peroxide Decomposition by Chlorinated Compounds , 1964 .

[25]  C. Klots.  Statistical Theory of Kinetic Energy of Fragmentation in Certain Unimolecular Dissociations , 1964 .

[26]  G. Whitten,et al.  Accurate and Facile Approximation for Vibrational Energy‐Level Sums , 1963 .

[27]  G. Kohlmaier,et al.  Collisional Transition Probabilities for Vibrational Deactivation of Chemically Activated sec‐Butyl Radicals. Diatomic and Polyatomic Molecules , 1963 .

[28]  Kang Yang.  Free Radical Reactions Initiated by Ionizing Radiation. II. Rate Constants for Hydrogen Atom Addition Reactions with Mono-olefins, Butadiene and Benzene , 1962 .

[29]  S. J. Strickler,et al.  Relationship between Absorption Intensity and Fluorescence Lifetime of Molecules , 1962 .

[30]  D. Christensen,et al.  Infrared absorption spectra of deuterated vinyl fluorides , 1958 .

[31]  B. Bohmfalk,et al.  Reaction Heats of Organic Halogen Compounds. IV. A High Temperature Calorimeter and the Hydrogenation of Methyl, Ethyl, and Vinyl Chlorides , 1956 .

[32]  R. Marcus.  Unimolecular dissociations and free radical recombination reactions , 1952 .

[33]  R. J. Bell,et al.  Introductory Fourier transform spectroscopy , 1972 .

[34]  Ian W. M. Smith,et al.  Infra-red chemiluminescence from vibrationally excited CO. Part 2.—Product distribution from the reaction O + CS → CO + S , 1972 .

[35]  J. Knox,et al.  Activated chloroalkyl radicals in the chlorination of trichloroethylene and other olefins , 1969 .

[36]  J. Knox,et al.  The rate of addition of hydrogen atoms to olefins: Isobutane and ethylene , 1969 .

[37]  F. Dainton,et al.  Photochlorination studies. Part 8.—Competitive photochlorination in mixtures of cis-1, 2-dichloroethylene with (a) vinyl chloride and (b) trichloroethylene , 1962 .

[38]  T. L. Cottrell.  The strengths of chemical bonds , 1958 .

[39]  G. Herzberg,et al.  Spectra of diatomic molecules , 1950 .